Burak Ulgut

XPS enables visualization of electrode potential screening in an ionic liquid medium with temporal- and lateral-resolution

We 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.

In-Situ XPS Monitoring and Characterization of Electrochemically Prepared Au Nanoparticles in an Ionic Liquid

Gold 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.

Optical and XPS evidence for the electrochemical generation of an N-heterocyclic carbene and its CS2 adduct from the ionic liquid [bmim][PF6]

Room 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.

Lyotropic Liquid Crystalline Mesophase of Sulfuric Acid–Nonionic Surfactant Stabilizes Lead(II) Oxide in Sulfuric Acid Concentrations Relevant to Lead Acid Batteries

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.

DC Electrowetting of Nonaqueous Liquid Revisited by XPS

Liquid poly(ethylene glycol) (molecular weight, ∼600 Da) with a low vapor pressure is used as droplets in an ultrahigh-vacuum X-ray photoelectron spectrometer (XPS) chamber with traditional electrowetting on dielectric (EWOD) device geometry. We demonstrate that, using XPS data, independent of the sign of the applied voltage, the droplet expands on the substrate with the application of a nonzero voltage and contracts back when the voltage is brought back to zero. However, the main focus of the present investigation is about tracing the electrical potential developments on and around the droplet, using the shifts in the binding energy positions of the core levels representative of the liquid and/or the substrate in an noninvasive and chemically specific fashion, under imposed electrical fields, with an aim of shedding light on numerous models employed for simulating EWOD phenomenon, as well as on certain properties of liquid/solid interfaces. While the lateral resolution of XPS does not permit to interrogate the interface directly, we explicitly show that critical information can be extracted by probing both sides of the interface simultaneously under external bias in the form of potential steps or direct current. We find that, even though no potential drop is observed at the metal-wire electrode/liquid interface, the entire potential drop develops across the liquid/solid-substrate interface, which is faster than our probe time window (∼100 ms) and is promptly complying with the applied bias until breakdown. No indication of band bending nor additional broadening can be observed in the C 1s peak of the liquid, even under electrical field strengths exceeding 107 V/m. Moreover and surprisingly, the liquid recovers within seconds after each catastrophic breakdown. All of these findings are new and expected to contribute significantly to a better understanding of certain physicochemical properties of liquid/solid interfaces.

Synthesis of mesoporous LiMn2O4 and LiMn2−xCoxO4 thin films using the MASA approach as efficient water oxidation electrocatalysts

Mesoporous, highly active, robust, and cost-effective thin films are in big demand for water splitting by electrocatalysis. Molten-salt assisted self-assembly (MASA) is an effective method to synthesize mesoporous thin films. Transparent clear solutions of salts (LiNO3 and [Mn(H2O)6](NO3)2), acid (HNO3), and surfactants (CTAB and P123) can be spin-coated over substrates as liquid crystalline (LC) films and calcined to obtain mesoporous high quality transparent thin films. A mixture of three salts (LiNO3, [Mn(H2O)6](NO3)2, and [Co(H2O)6](NO3)2) also forms LC mesophases that can be calcined to produce mesoporous nanocrystalline mixed metal lithiates (meso-LiMn2−xCoxO4) with surface areas as large as 144 m2 g−1 (for LiMn1.5Co0.5O4). The synergic effects of these salts improve the pore-size of the final products; the pore size drops from around 11 nm (in the meso-LiMn2O4) to 6–7 nm in the meso-LiMn1−xCoxO4. The meso-LiMn2−xCoxO4 films were tested at pH 13.6 as water oxidation electrocatalysts over a broad range of x. While meso-LiMn2O4 shows a low activity towards water oxidation, the catalytic activity increases with the increasing Co(III) content of the films. The highest mass activity per cobalt, 1744 A g−1, is obtained for meso-LiMnCoO4, which remains as a robust and efficient film even at a current density of 120 mA cm−2.

XPS investigation of the vacuum interface of an ionic liquid under triangular electrical excitation for slow transients

We report on an XPS investigation of slow transient charge imbalance at the vacuum interface of an ionic liquid, by imposing a triangular electrical excitation to two gold electrodes having an ionic liquid in between. Intensity ratio of the two N 1s peaks of the anion and the cation undergoes a total difference of up to ∼20% as the IL is slowly electrified between −5 to +5 V.