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.
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.
Under application of a voltage bias, asymmetric ion movement of an ionic liquid (IL) through a multilayered graphene (MLG) electrode has been detected by X-ray photoelectron spectroscopy, via recording the intensity of the two nitrogen peaks. Accordingly, we observe that upon increasing the bias, the two peaks representing the cationic and anionic fragments of the IL start appearing with increasing intensity, together with an asymmetry in their ratio, differing from unity by about 10%. Bias-dependent binding energy shifts followed through atomic features of the IL (F 1s, N 1s, and C 1s) and the graphene electrode (C 1s) indicate that a distinct solid−liquid interface develops throughout the entire intercalation process with an additional and pertinent evidence for finite potential drops across the two electrical double layers. This evidence is bolstered by the fact that the measured binding energy difference between the F 1s of the liquid and C 1s peak of the semisolid MLG electrode is only about half of the applied bias, where the rest of the applied voltage is screened by the two electrical double layers at the solid−liquid interfaces between (i) the MLG−IL and (ii) IL−bottom metal electrode. A simple electrostatic estimation indicates that even this small 10% ion imbalance would lead to 4 orders of magnitude larger voltage development between the IL and the MLG phases and suggests the need for amendment(s) to the current understanding of the dielectric description of ILs.
Rough structures with re-entrant property and their subsequent surface energy reduction with long-chain fluorocarbon oligomers are both critical in developing superamphiphobic (SAP, i.e. both super hydrophobic and superoleophobic) surfaces. However, morphology of the lowsurface energy layer on a rough re-entrant substrate can strongly depend on the fluorocarbon oligomers used. In this study, the effect of polar end of different kinds of long-chain fluorocarbon oligomers in promoting a self-assembled monolayer with close packed molecules and robust adhesion on multi-scale rough Al alloy surfaces was investigated. Hierarchical Al alloy surfaces with microgrooves and nanograss structures were developed by a simple combination of one-directional mechanical sanding and post treatment in boiling de-ionized
Thin deposits of aligned semiconducting titanium oxide and of zinc oxide nanowires are prepared by grazing incidence spraying on transparent substrates. By measuring the transmittance of linearly polarized light of...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.