Browsing by Author "Ulgut, B."
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Item Open Access In-Situ XPS monitoring and characterization of electrochemically prepared Au nanoparticles in an ionic liquid(American Chemical Society, 2017) Camci, M. T.; Ulgut, B.; Kocabas, C.; Süzer, ŞefikGold nanoparticles (Au NPs) have been electrochemically prepared in situ and in vacuo using two different electrochemical device configurations, containing an ionic liquid (IL), N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, that serves both as reaction and as stabilizing media for the NPs. It was observed in both devices that Au NPs were created using an anodically triggered route. The created Au NPs are relatively small (3-7 nm) and reside within the IL medium. X-ray photoelectron spectroscopy is utilized to follow not only the formation of the NPs but also their charging/discharging properties, by monitoring the charging shifts of the Au4f peak representing the electrodes and also the Au NPs as well as the F1s peak of the IL after polarizing one of the electrodes. Accordingly, DC polarization across the electrodes leads to a uniform binding energy shift of F1s of the IL along with that of Au4f of the NPs within. Moreover, this shift corresponds to only half of the applied potential. AC polarization brings out another dimension for demonstrating further the harmony between the charging/discharging property of the IL medium and the Au NPs in temporally and laterally resolved fashions. Polarization of the electrodes result in perfect spectral separation of the Au4f peaks of the NPs from those of the metal in both static (DC) and in time- and position-dependent (AC) modes.Item Open Access Lyotropic liquid crystalline mesophase of sulfuric acid − nonionic surfactant stabilizes lead (II) oxide in sulfuric acid concentrations relevant to lead acid batteries(American Chemical Society, 2017) Uzundal, C. B.; Balci, F. M.; Ulgut, B.; Dag, Ö.Concentrated sulfuric acid (SA) and nonionic surfactant (C12H25(OCH2CH2)10OH, C12E10) form lyotropic liquid crystalline (LLC) mesophases in a broad range of SA concentrations; the SA/C12E10 mole ratio may vary from 2 to 11 in the LLC mesophases in the presence of a small amount of water. The mesophase is hexagonal at low SA concentration and cubic at higher concentrations. Three different compositions were prepared (one hexagonal and two cubic) with the SA/C12E10 mole ratio of 2.5, 6, and 9, denoted as 2.5LC, 6LC, and 9LC, respectively. They all display electrochemical SA activity in Pt and Pb systems. Most interestingly, they show the electrochemical formation of stable PbO species in a deeply acidic medium as evidenced by the X-ray diffraction, cyclic voltammetry, and linear sweep voltammetry experiments. The preferable properties of PbO over PbSO4 for lead acid batteries (LABs) make it uniquely positioned as a superior gel electrolyte for the LABs that would mitigate sulfation.Item Open Access Optical and XPS evidence for the electrochemical generation of an n-heterocyclic carbene and its CS2 adduct from the ionic liquid [bmim][PF6](Royal Society of Chemistry, 2017) Gokturk, P. A.; Donmez, S. E.; Ulgut, B.; Türkmen, Y. E.; Süzer, ŞefikRoom temperature ionic liquids continue to be at the forefront of chemistry, covering a broad spectrum of research areas from electrochemistry and energy to catalysis and green chemistry. Therefore, it is of great value to fully understand the chemical and electrochemical reactivity and stability of ionic liquids utilized in these applications. In this context, we have investigated the electrochemical generation of an N-heterocyclic carbene and its CS2 adduct from the ionic liquid [bmim][PF6], and X-ray photoelectron spectroscopy (XPS) proved to be a highly effective spectroscopic tool to study such systems. Initially, the dithiocarboxylate adduct was chemically synthesized as a reference compound starting from both [bmim][PF6] and [bmim][OAc], and characterized by HRMS, and 1H- and 13C-NMR, FTIR, visible and X-ray photoelectron spectroscopy. While a simple mixture of [bmim][PF6] and CS2 revealed no evidence of adduct formation, the application of an electrochemical stimulus led to the formation of the dithiocarboxylate adduct as evidenced optically and through the newly formed S2p peak in the XP spectrum. Further evidence for the electrochemical reduction of [bmim][PF6] to the corresponding N-heterocyclic carbene came from the XPS analysis via the appearance of a new N1s peak in the XP spectrum.Item Open Access XPS enables visualization of electrode potential screening in an ionic liquid medium with temporal-and lateral-resolution(Royal Society of Chemistry, 2016) Camci, M. T.; Aydogan, P.; Ulgut, B.; Kocabas, C.; Süzer, ŞefikWe present an X-ray photoelectron spectroscopic (XPS) investigation of potential screening across two gold electrodes fabricated on a porous polymer surface which is impregnated with the ionic liquid (IL) N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide [DEME-TFSI]. The IL provides a sheet of conducting layers to the insulating polymer film, and allows monitoring charging and screening dynamics at the polymer + IL/vacuum interface in a laterally resolved fashion across the electrodes. Time-resolved measurements are also implemented by recording F1s peaks of the IL, while imposing 10 mHz square-wave (SQW) pulses across the two electrodes in a source-drain geometry. Variations in the F1s binding energy reflect directly the transient local electrical potential, and allow us to visualize screening of the otherwise built-in local voltage drop on and across the metal electrodes in the range of millimeters. Accordingly, the device is partitioned into two oppositely polarized regions, each following polarization of one electrode through the IL medium. On the other extreme, upon imposing relatively fast 1 kHz SQW pulses the charge screening is prevented and the device is brought to assume a simple resistor role. A simple equivalent circuit model also reproduces the observed voltage transients qualitatively. The presented structure and variants of XPS measurements, enabling us to record voltage transients in unexpectedly large lateral distances away from the electrodes, can impact the understanding of various electrochemical concepts.Item Open Access XPS studies of SiO2/Si system under external bias(American Chemical Society, 2003) Ulgut, B.; Süzer, ŞefikThermally grown SiO2 layers on Si (100) substrate have been subjected to different external voltage bias during XPS analysis to induce changes in the measured binding energy difference between Si4+ and Si0 in Si2p and SiKLL regions. The Si2pp binding energy difference increases from 3.2 to 4.8 for samples containing 1-7 nm oxide thickness, and furthermore, this difference can be influenced by application of an external bias to the sample. Application of negative d.c. bias increases the binding energy difference, whereas positive bias decreases it. The voltage dependence of the binding energy difference exhibits a sigmoid character with an abrupt change near 0 V. Both the binding energy difference and differential change between the positive and negative bias have similar functional dependence on the thickness. This is attributed to differential charging between the silicon oxide layer and silicon substrate, which is decreased when a positive bias is applied to the sample (and therefore attracting a larger proportion of the stray electrons from the vacuum chamber to partially neutralize the oxide). Similarly, when negative bias is applied, the stray electrons are repelled from the sample resulting in less neutralization and an increased differential charging. Through external biasing, it is determined that charging in the SiO2/Si system persists all of the way down to 1 nm. Application of a.c. (square-wave) bias is equivalent to simultaneous application of negative and positive bias together. However, the differential change in the binding energy difference in the positive and negative cycle is frequency dependent and approaches to the d.c. results at lower frequencies.Item Open Access XPS-evidence for in-situ electrochemically-generated carbene formation(Elsevier Ltd., 2017) Gokturk, A. P.; Salzner, U.; Nyulászi, L.; Ulgut, B.; Kocabas, C.; Süzer, ŞefikStable N-heterocyclic carbenes (NHC) are a class of compounds that has attracted a huge amount of interest in the last decade. One way to prepare NHCs is through chemical or electrochemical reduction of 1,3-disubstituted imidazolium cations. We are presenting an in-situ electrochemical X-ray Photoelectron Spectroscopy (XPS) study where electrochemically reduced imidazolium cations lead to production of stable NHC. The electroactive imidazolium species is not only the reactant, but also part of the ionic liquid which serves as the electrolyte, the medium and the electroactive material. This allows us to directly probe the difference between the parent imidazolium ion and the NHC through the use of XPS. The interpretation of the results is supported by both observation of reversible redox peaks in the voltammogram and the density functional theory calculations.Item Open Access Zero-free-parameter modeling approach to predict the voltage of batteries of different chemistries and supercapacitors under arbitrary load(Electrochemical Society, Inc., 2017) Özdemir, E.; Uzundal, C. B.; Ulgut, B.Performance modeling of electrochemical energy storage systems is gathering increasingly higher attention in recent years. With the ever increasing power demand of mobile applications, predicting voltage behavior under different load profiles is of utmost importance for communications, automotive and consumer electronics. The ideal modelling approach needs not only to accurately predict the response of the battery, but also be robust, easy to implement and have low computational complexity. We will present a new algorithm that is algebraically straightforward, that has no adjustable parameters and that can accurately predict the voltage response of batteries and supercapacitors. The approach works well in a variety of discharge profiles ranging from simple long DC discharge/charge profiles to pulse schemes based on drive schedules published by regulatory bodies. Our approach is based on Electrochemical Impedance Spectroscopy measurements done on the system to be predicted. The spectrum is used in the frequency domain without any further processing to predict the fast moving portion of the voltage in the frequency domain. DC response is added in through a straightforward lookup table. This widely applicable approach can predict the voltage of with less than 1% error, without any adjustable parameters to a large variety of discharge profiles.