Browsing by Subject "Adsorption"

Now showing 1 - 20 of 62

Open Access
Ab initio temperature dependent studies of the homoepitaxial growth on Si(0 0 1) surface
(2001) Dağ, S.; Çıracı, Salim; Kılıç, Ç.; Fong, C. Y.
We performed ab initio zero temperature and finite temperature molecular dynamics calculations to investigate the homoepitaxial growth on the Si(0 0 1) surface. How do the deposited atoms (adatoms) form addimers and how do the addimers reach their favorable positions at the nucleation site of the growth process are presented. Once two epitaxial addimers, one over the dimer row and oriented perpendicular to the surface dimer bonds and the other over the adjacent trough, are aligned at high temperature, the nucleation site of the growth process is formed. The concerted bond exchange between these addimers and the reconstructed surface dimers is found to be the atomistic mechanism that leads to the homoepitaxial growth. © 2001 Elsevier Science B.V.
Open Access
Adsorption behavior of radionuclides, 137Cs and 140Ba, onto solid humic acid
(Springer, 2011) Çelebi, O.; Erten, Hasan N.
In this research, the adsorption behaviors of two important fission product radionuclides (137Cs and 133Ba) onto sodium form of insolubilized humic acid (INaA) were investigated as a function of time, cation concentration and temperature, utilizing radiotracer method. The resulting data was fitted well to the Freundlich and Dubinin-Radushkevich (D-R) isotherms. Thermodynamic constants such as; free energy (ΔGads), enthalpy (ΔHads), entropy (ΔSads) of adsorption were determined. Temperature change didn't effect sorption processes significantly. Best fitting kinetic models were found for a better understanding of adsorption mechanisms. It was found that Ba2+ was adsorbed five times more than Cs+ onto structurally modified humic acid and kinetic studies indicated that adsorption behaviors of both ions obey the pseudo second order rate law. The effect of pH changes on adsorption was also examined and optimum pH range was found in the range of pH 6-8. FTIR and solid state carbon nmr (13CNMR) spectroscopic techniques were used to understand the structural changes during insolubilization process. Quantitative determination of adsorption sites was carried out using potentiometric titration method and the resulting data was treated by using appropriate Gran functions.
Open Access
Adsorption of group IV elements on graphene, silicene, germanene and stanene: dumbbell formation
(ACS Publications, 2014-12-09) Ozcelik, V. O.; Kecik, D.; Durgun, Engin; Çıracı, Salim
Silicene and germanene derivatives constructed from periodic dumbbell units play a crucial role in multilayers of these honeycomb structures. Using first-principles calculations based on density functional theory, here we investigate the dumbbell formation mechanisms and energetics of Group IV atoms adsorbed on graphene, silicene, germanene and stanene monolayer honeycomb structures. The stabilities of the binding structures are further confirmed by performing ab-initio molecular dynamics calculations at elevated temperatures, except for stanene which is subject to structural instability upon the adsorption of adatoms. Depending on the row number of the adatoms and substrates we find three types of binding structures, which lead to significant changes in the electronic, magnetic, and optical properties of substrates. In particular, Si, Ge and Sn adatoms adsorbed on silicene and germanene form dumbbell structures. Furthermore, dumbbell structures occur not only on single layer, monatomic honeycomb structures, but also on their compounds like SiC and SiGe. We show that the energy barrier to the migration of a dumbbell structure is low due to the concerted action of atoms. This renders dumbbells rather mobile on substrates to construct new single and multilayer Si and Ge phases.
Open Access
Adsorption site of alkali metal overlayers on Si(001) 2 × 1
(1992) Batra, I. P.; Çıracı, Salim
The alkali metal semiconductor interfaces are currently being investigated by a variety of tools. Most studies to date at half a monolayer coverage have shown preference for either a quasi-hexagonal (H) site or a long-bridge (B) site. At this coverage one-dimensional chain structure for K on Si(001) 2 × 1 have now been confirmed by scanning tunneling microscopy (STM). The data, however, is consistent with either of the two sites. STM investigations at low coverages suggested that alkali metals like K and Cs occupy a novel site, Y, which is a bridge site between two Si atoms belonging to different dimers along the dimer row [110] direction. The total energy calculations for this new Y site, discovered by STM, have shown that it is indeed a site of (local) energy minimum. The ability of the surface silicon atoms, which are not adjacent to the alkali metal atom, to buckle makes the Y site a competitive adsorption site. We deduce the nature of bonding between alkali metals and Si using the STM data. It is concluded that the bond is substantially ionic in nature. © 1992.
Open Access
A characterization study of some aspects of the adsorption of aqueous Co2+ ions on a natural bentonite clay
(Academic Press, 2006-06-13) Shahwan, T.; Erten, H. N.; Unugur, S.
The natural bentonite used in this study contained montmorillonite in addition to low cristobalite. The uptake of aqueous Co2+ ions was investigated as a function of time, concentration, and temperature. In addition, the change in the interlayer space of montmorillonite was analyzed using XRPD, and the distribution of fixed Co2+ ions on the heterogeneous clay surface was recorded using EDS mapping. The sorbed amount of Co2+ appeared to closely follow Freundlich isotherm, with the sorption process showing apparent endothermic behavior. The relevance of the apparent _Ho values is briefly discussed. Analysis of the Co-sorbed bentonite samples using SEM/EDS showed that the montmorillonite fraction in the mineral was more effective in Co2+ fixation than the cristobalite fraction. XRPD analysis demonstrated that the interlayer space of montmorillonite was slightly modified at the end of sorption.
Open Access
A comparative study of O2 adsorbed carbon nanotubes
(2003) Dag, S.; Gülseren, O.; Çıracı, Salim
First-principles, density functional calculations show that O2 adsorbed single-wall carbon nanotubes (SWNT) show dramatic differences depending on the type of the tube. Upon O2 physisorption, the zig-zag SWNT remains semiconducting, while the metallicity of the armchair is lifted for the spin-down bands. The spin-up bands continue to cross at the Fermi level, and make the system metallic only for one type of spin. The singlet bound state of O2 occurs at the bridge site of the (6,6) SWNT at small distance from the surface of the tube. However, for the hollow site, the molecule dissociates when it comes close to the surface. © 2003 Elsevier B.V. All rights reserved.
Open Access
Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons
(Academic Press Inc., 2017) Topuz, F.; Uyar, T.
Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitous environmental contaminants, and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65 mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon.
Open Access
Development of superhydrophobic electrospun fibrous membrane of polymers of intrinsic microporosity (PIM-2)
(Elsevier, 2018) Satılmış, Bekir; Uyar, Tamer
Polymers of intrinsic microporosity (PIMs) are increasingly recognized as a potential membrane material for adsorption and separation applications due to their permanent porosity and solution processability. PIM-2 can be produced using commercially available 5,5′,6,6′-Tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane and decafluorobiphenyl monomers in the powder form. It possesses considerable amount of fluorine in the polymer backbone and this feature could provide significant hydrophobicity to polymer. This research aims to investigate the fabrication of self-standing PIM-2 fibrous membranes by electrospinning method to introduce a useful material for adsorption applications. Electrospinning was performed using tetrachloroethane as a solvent and beadfree, uniform fibers were produced as confirmed by SEM imaging. Average fiber diameter was calculated as 5.5 ± 1.5 μm for a self-standing fibrous membrane of PIM-2. Structural characterization was conducted using FT-IR, NMR and XPS spectroscopies showing the purity of pristine powder and fibrous membrane of PIM-2. Thermal stability of PIM-2 fibrous membrane was investigated using TGA and it shows no discernible weight loss below 450 °C. The porosity of fibrous membrane was investigated by N2 adsorption/desorption measurements that indicates significant microporosity with ∼600 m2 g−1 BET surface area. In addition, the hydrophobicity of PIM-2 was tested by water contact angle measurements, showing 155 ± 6° WCA, indicating superhydrophobicity owing to rough surface and high fluorine content. Consequently, the combination of straightforward synthesis, solution processability, high thermal stability, high surface area, and superhydrophobicity makes PIM-2 a promising candidate for adsorption applications. Therefore, it was successfully employed in organic and oil adsorption. Fibrous membranes of PIM-2 has shown up to 2200 ± 100% and 1900 ± 100% weight gain after in contact with silicon oil and DMSO respectively. In addition, dense membrane of PIM-2 was prepared by solvent casting method and the uptake ability was compared with fibrous membrane showing that fibrous form is more convenient for liquid adsorption applications.
Open Access
Direct evidence for the instability and deactivation of mixed-oxide systems: influence of surface segregation and subsurface diffusion
(2011) Emmez, E.; Vovk, E. I.; Bukhtiyarov V. I.; Ozensoy, E.
In the current contribution, we provide a direct demonstration of the thermally induced surface structural transformations of an alkaline-earth oxide/transition metal oxide interface that is detrimental to the essential catalytic functionality of such mixed-oxide systems toward particular reactants. The BaOx/TiO2/Pt(111) surface was chosen as a model interfacial system where the enrichment of the surface elemental composition with Ti atoms and the facile diffusion of Ba atoms into the underlying TiO2 matrix within 523 873 K leads to the formation of perovskite type surface species (BaTiO3/Ba2TiO4/BaxTiyOz). At elevated temperatures (T > 973 K), excessive surface segregation of Ti atoms results in an exclusively TiO2/TiOx-terminated surface which is almost free of Ba species. Although the freshly prepared BaOx/TiO2/Pt(111) surface can strongly adsorb ubiquitous catalytic adsorbates such as NO2 and CO2, a thermally deactivated surface at T > 973 K practically loses all of its NO2/CO2 adsorption capacity due to the deficiency of surface BaOx domains.
Open Access
Effects of laser ablated silver nanoparticles on Lemna minor
(Elsevier, 2014) Üçüncü, E.; Özkan, A. D.; Kurşungöz, C.; Ülger, Z. E.; Ölmez, T. T.; Tekinay, T.; Ortaç, B.; Tunca E.
Open Access
Effects of silicon and germanium adsorbed on graphene
(A I P Publishing LLC, 2010) Aktürk, E.; Ataca, C.; Çıracı, Salim
Based on the first-principles plane wave calculations, we studied the adsorption of Si and Geon graphene. We found that these atoms are bound to graphene at the bridge site with a significant binding energy, while many other atoms are bound at the hollow site above the center of hexagon. It is remarkable that these adatoms may induce important changes in the electronic structure of graphene even at low coverage. Semimetallic graphene becomes metallized and attains a magnetic moment. The combination of adatom orbitals with those of ππ- and π∗π∗-states of bare graphene is found responsible for these effects.
Open Access
Electroless synthesis of 3nm wide alloy nanowires inside Tobacco mosaic virus
(2012) Balci, S.; Hahn, K.; Kopold P.; Kadri, A.; Wege, C.; Kern, K.; Bittner, A.M.
We show that 3nm wide cobaltiron alloy nanowires can be synthesized by simple wet chemical electroless deposition inside tubular Tobacco mosaic virus particles. The method is based on adsorption of Pd(II) ions, formation of a Pd catalyst, and autocatalytic deposition of the alloy from dissolved metal salts, reduced by a borane compound. Extensive energy-filtering TEM investigations at the nanoscale revealed that the synthesized wires are alloys of Co, Fe, and Ni. We confirmed by high-resolution TEM that our alloy nanowires are at least partially crystalline, which is compatible with typical Co-rich alloys. Ni traces bestow higher stability, presumably against corrosion, as also known from bulk CoFe. Alloy nanowires, as small as the ones presented here, might be used for a variety of applications including high density data storage, imaging, sensing, and even drug delivery. © 2012 IOP Publishing Ltd.
Open Access
Elucidating the barriers on direct water splitting: key role of oxygen vacancy density and coordination over PbTiO3 and TiO2
(American Chemical Society, 2021-01-28) Ersen, M.; Ellialtıoğlu, Ş.; Gülseren, Oğuz; Uner, D.
In this work, using the state-of-the-art first-principles calculations based on density functional theory, we found that the concentration and coordination of surface oxygen vacancies with respect to each other were critical for the direct water-splitting reaction on the (001) surfaces of PbTiO3 and TiO2. For the water-splitting reaction to happen on TiO2-terminated surfaces, it is necessary to have two neighboring O vacancies acting as active sites that host two adsorbing water molecules. However, eventual dissociation of O–H bonds is possible only in the presence of an additional nearest-neighbor O vacancy. Unfortunately, this necessary third vacancy inhibits the formation of molecular hydrogen by trapping the dissociated H atoms on TiO2-terminated surfaces. Formation of up to three O vacancies is energetically less costly on both terminations of PbTiO3(001) surfaces compared with those on TiO2; the presence of Pb leads to weaker O bonds over these surfaces. Molecular hydrogen formation is more favorable on the PbO-terminated surface of PbTiO3, requiring only two neighboring oxygen vacancies. However, the hydrogen molecule is retained near the surface by weak van der Waals forces. Our study indicates two barriers leading to low productivity of direct water-splitting processes. First and foremost, there is an entropic barrier imposed by the requirement of at least two nearest-neighbor O vacancies, sterically hindering the process. Furthermore, there are also enthalpic barriers of formation on TiO2-terminated surfaces or removal of H2 molecules from the PbO-terminated surface. The requirement dictating three nearest-neighbor oxygen vacancies for hydrogen evolution is also consistent with the chemical intuition: The nearest neighbor of the formed hydrogen should be reduced enough to inhibit spontaneous oxidation under ambient conditions.
Open Access
Energetics and Electronic Structures of Individual Atoms Adsorbed on Carbon Nanotubes
(American Chemical Society, 2004) Durgun, Engin; Dag, S.; Çıracı, Salim; Gülseren, O.
The adsorption of individual atoms on the semiconducting and metallic single-walled carbon nanotubes (SWNT) has been investigated by using the first principles pseudopotential plane wave method within density functional theory. The stable adsorption geometries and binding energies have been determined for a large number of foreign atoms ranging from alkali and simple metals to the transition metals and group IV elements. We have found that the character of the bonding and associated physical properties strongly depends on the type of adsorbed atoms, in particular, on their valence electron structure. Our results indicate that the properties of SWNTs can be modified by the adsorbed foreign atoms. Although the atoms of good conducting metals, such as Zn, Cu, Ag, and Au, form very weak bonds, transition-metal atoms such as Ti, Sc, Nb, and Ta and group IV elements C and Si are adsorbed with a relatively high binding energy. Owing to the curvature effect, these binding energies are larger than the binding energies of the same atoms on the graphite surface. We have showed that the adatom carbon can form strong and directional bonds between two SWNTs. These connects can be used to produce nanotube networks or grids. 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 ID nanomagnets or nanoconductors, conducting connects, and so forth.
Open Access
Enhancement of formic acid dehydrogenation selectivity of Pd(111) single crystal model catalyst surface via Brønsted bases
(American Chemical Society, 2019) Karakurt, Bartu; Koçak, Yusuf; Özensoy, Emrah
The influence of ammonia (NH3) on the doubly deuterated formic acid (DCOOD, FA) dehydrogenation selectivity for a Pd(111) single crystal model catalyst surface was investigated under ultrahigh vacuum conditions using temperature-programmed desorption and temperature-programmed reaction spectroscopy techniques. NH3 adsorption on Pd(111) revealed reversible, molecular desorption without any significant decomposition products, while DCOOD adsorption on Pd(111) yielded D2, D2O, CO, and CO2 as a result of dehydration and dehydrogenation pathways. Functionalizing the Pd(111) surface with ammonia suppressed the FA dehydration and enhanced the dehydrogenation pathway. The boost in the FA dehydrogenation of Pd(111) in the presence of NH3 can be linked to the ease of FA deprotonation as well as the stabilization of the decomposition intermediate (i.e., formate) due to the presence of ammonium counterions on the surface. In addition, the presence of a H-bonded ammonia network on the Pd(111) surface increased the hydrogen atom mobility and decreased the activation energy for molecular hydrogen desorption. In the presence of NH3, catalytic FA decomposition on Pd(111) also yielded amidation reactions, which further suppressed CO liberation and prevented poisoning of the Pd(111) active sites due to strongly bound CO species.
Open Access
Fabrication of cellulose acetate/polybenzoxazine cross-linked electrospun nanofibrous membrane for water treatment
(Elsevier, 2017-12) Ertaş, Yelda; Uyar, Tamer
Herein, polybenzoxazine based cross-linked cellulose acetate nanofibrous membrane exhibiting enhanced thermal/mechanical properties and improved adsorption efficiency was successfully produced via electrospinning and thermal curing. Initially, suitable solution composition was determined by varying the amount of the benzoxazine (BA-a) resin, cellulose acetate (CA) and citric acid (CTR) to obtain uniform nanofibrous membrane via electrospinning. Subsequently, thermal curing was performed by step-wise at 150, 175, 200 and 225 °C to obtain cross-linked composite nanofibrous membranes. SEM images and solubility experiments demonstrated that most favorable result was obtained from the 10% (w/v) CA, 5% (w/v) BA-a and 1% (w/v) CTR composition and cross-linked nanofibrous membrane (CA10/PolyBA-a5/CTR1) was obtained after the thermal curing. Chemical structural changes (ring opening) occurred by thermal curing revealed successful cross-linking of BA-a in the composite nanofibrous membrane. Thermal, mechanical and adsorption performance of pristine CA and CA10/PolyBA-a5/CTR1 nanofibrous membranes were studied. Char yield of the pristine CA nanofibrous membrane has increased notably from 12 to 24.7% for composite CA10/PolyBA-a5/CTR1 membrane. When compared to pristine CA membrane, CA10/PolyBA-a5/CTR1 nanofibrous membrane has shown superior mechanical properties having tensile strength and Young's modulus of 8.64 ± 0.63 MPa and 213.87 ± 30.79 MPa, respectively. Finally, adsorption performance of pristine CA and CA10/PolyBA-a5/CTR1 nanofibrous membranes was examined by a model polycyclic aromatic hydrocarbon (PAH) compound (i.e. phenanthrene) in aqueous solution, in which CA10/PolyBA-a5/CTR1 nanofibrous membrane has shown better removal efficiency (98.5%) and adsorption capacity (592 μg/g).
Open Access
Fe promoted NOx storage materials: structural properties and NOx uptake
(American Chemical Society, 2010) Kayhan, E.; Andonova, S. M.; Şentürk, G. S.; Chusuei, C. C.; Ozensoy, E.
Fe promoted NOx storage materials were synthesized in the form of FeOx/BaO/Al2O3 ternary oxides with varying BaO (8 and 20 wt %) and Fe (5 and 10 wt %) contents. Synthesized NOx storage materials were investigated via TEM, EELS, BET, FTIR, TPD, XRD, XPS, and Raman spectroscopy, and the results were compared with the conventional BaO/Al2O3 NOx storage system. Our results suggest that the introduction of Fe in the BaO/Al2O3 system leads to the formation of additional NOx storage sites which store NOx mostly in the form of bidentate nitrates. NO2 adsorption experiments at 323 K via FTIR indicate that, particularly in the early stages of the NOx uptake, the NOx storage mechanism is significantly altered in the presence of Fe sites where a set of new surface nitrosyl and nitrite groups were detected on the Fe sites and the surface oxidation of nitrites to nitrates is significantly hindered with respect to the BaO/Al2O3 system. Evidence for the existence of both Fe3+ as well as reduced Fe2+/(3-x)+ sites on the freshly pretreated materials was detected via EELS, FTIR, Raman, and XRD experiments. The influence of the Fe sites on the structural properties of the synthesized materials was also studied by performing ex situ annealing protocols within 323-1273 K followed by XRD and Raman experiments where the temperature dependent changes in the morphology and the composition of the surface domains were analyzed in detail. On the basis of the TPD data, it was found that the relative stability of the stored NOx species is influenced by the morphology of the Ba and Fe containing NOx-storage domains. The relative stabilities of the investigated NOx species were found to increase in the following order: N2O3/NO+ < nitrates on γ-Al2O3 < surface nitrates on BaO < bidentate nitrates on FeOx sites < bulk nitrates on BaO.
Open Access
Femtosecond response of J aggregates adsorbed onto silver colloid surfaces
(2003) Yaǧlioǧlu G.; Dorsinville, R.; Özçelik, S.
The observation of stimulated emission from J aggregates adsorbed onto silver colloid surfaces using femtosecond excitation was reported. The stimulated emission was inferred from the excitation intensity and wavelength dependence of the emission band. The stimulated emission originated from the amplification of the one-exciton state emission by an induced transition from the two-exciton state to the one-exciton state.
Open Access
Finite temperature studies of Te adsorption on Si(0 0 1)
(Elsevier, 2002) Sen, P.; Çıracı, Salim; Batra, I. P.; Grein, C. H.; Sivananthan, S.
We perform first principles density functional calculations to investigate the adsorption of Te on the Si(0 0 1) surface from low coverage up to a monolayer coverage. At low coverage, a Te atom is adsorbed on top of the Si surface dimer bond. At higher coverages, Te atoms adsorption causes the Si-Si dimer bond to break, lifting the (2 × 1) reconstruction. We find no evidence of the Te-Te dimer bond formation as a possible source of the (2 × 1) reconstruction at a monolayer coverage. Finite temperature ab initio molecular dynamics calculations show that Te covered Si(0 0 1) surfaces do not have any definitive reconstruction. Vibrations of the bridged Te atoms in the strongly anharmonic potentials prevent the reconstruction structure from attaining any permanent, two-dimensional periodic geometry. This explains why experiments attempting to find a definite model for the reconstruction reached conflicting conclusions. © 2002 Elsevier Science B.V. All rights reserved.
Open Access
Formation of quantum structures on a single nanotube by modulating hydrogen adsorption
(American Physical Society, 2003) Gülseren, O.; Yildirim, T.; Çıracı, Salim
Using first-principles density functional calculations we showed that quantum structures can be generated on a single carbon nanotube by modulating the adsorption of hydrogen atoms. The band gap of the hydrogen-free zone of the tube widens in the adjacent hydrogen covered zone. The sudden variation of the band gap leads to band offsets at the conduction- and valence-band edges. At the end, the band gap of the whole system is modulated along the axis of the tube, which generates quantum wells or quantum dots. Specific electronic states are confined in these quantum wells. The type and radius of the nanotube and the extent and sequence of hydrogen-free and hydrogen-covered zones can provide several options to design a desired optoelectronic nanodevice.