Room-temperature ionic liquids are a new class of liquids with many important uses in electrical and electrochemical devices. The liquids are composed purely of ions in the liquid state with no solvent. They generally have good electrical and ionic conductivity and are electrochemically stable. Since their applications often depend critically on the interface structure of the liquid adjacent to the electrode, a molecular level description is necessary to understanding and improving their performance. There are currently no adequate models or descriptions on the organization of the ions, in these pure ionic compounds, adjacent to the electrode surface. In normal electrolytic solutions, the organization of solvent and ions is adequately described by the Gouy-Chapman-Sterns model. However, this model is based on the same concepts as those in Debye-Huckel theory, that is a dilute electrolyte, where ions are well-separated and noninteracting. This is definitely not the situation for ionic liquids. Thus our goal was to investigate the ionic liquid-metal interface using surface-specific vibrational spectroscopy sum frequency generation, SFG. This technique can probe the metal-liquid interface without interference from the bulk electrolyte. Thus the interface is probed in situ while the electrode potential is changed. To compliment the vibrational spectroscopy, electrochemical impedance spectroscopy (EIS) is used to measure the capacitance and estimate the "double layer" thickness and the potential of zero charge (PZC). In addition, the vibrational Stark shift of CO adsorbed on the Pt electrode was measured to provide an independent measure of the "double layer" thickness. All techniques were measured as a function of applied potential to provide full description of the interface for a variety of imidazolium-based (cation) ionic liquids. The vibrational Stark shift and EIS results suggest that ions organize in a Helmholtz-like layer at the interface, where the potential drop occurs over the a range of 3-5 A from the metal surface into the liquid. Further, the SFG results imply that the "double layer" structure is potential-dependent; At potentials positive of the PZC, anions adsorbed to the surface and the imidazolium ring are repelled to orient more along the surface normal, compared with the potentials negative of the PZC, at which the cation is oriented more parallel to the surface plane and the anions are repelled from the surface. The results present a view of the ionic liquid-metal electrode interface having a very thin "double layer" structure where the ions form a single layer at the surface to screen the electrode charge. However, the results also raise many other fundamental questions as to the detailed nature of the interfacial structure and interpretations of both electrochemical and spectroscopic data.
The generation of hydrogen from water using sunlight could potentially form the basis of a clean and renewable source of energy. Various water-splitting methods have been investigated previously, but the use of photocatalysts to split water into stoichiometric amounts of H2 and O2 (overall water splitting) without the use of external bias or sacrificial reagents is of particular interest because of its simplicity and potential low cost of operation. However, despite progress in the past decade, semiconductor water-splitting photocatalysts (such as (Ga1-xZnx)(N1-xOx)) do not exhibit good activity beyond 440 nm (refs 1,2,9) and water-splitting devices that can harvest visible light typically have a low solar-to-hydrogen efficiency of around 0.1%. Here we show that cobalt(II) oxide (CoO) nanoparticles can carry out overall water splitting with a solar-to-hydrogen efficiency of around 5%. The photocatalysts were synthesized from non-active CoO micropowders using two distinct methods (femtosecond laser ablation and mechanical ball milling), and the CoO nanoparticles that result can decompose pure water under visible-light irradiation without any co-catalysts or sacrificial reagents. Using electrochemical impedance spectroscopy, we show that the high photocatalytic activity of the nanoparticles arises from a significant shift in the position of the band edge of the material.
Vibrational spectroscopy, sum frequency generation, has been used to study the gas-liquid interface of imidazolium-based, room-temperature ionic liquids. The ionic liquids are divided into two categories on the basis of their miscibility with water, as hydrophobic (immiscible) and hydrophilic (miscible). The spectroscopy results indicate that water will reorient the cations of the hydrophobic ionic liquid, while in the hydrophilic ones they remain unaffected. Thus, under low water conditions the plane of the imidazolium ring remains parallel to the surface for both types of ionic liquid. However, at high water content the ring will reorient to along the surface normal for the hydrophobic ionic liquid but remain parallel to the surface for the hydrophilic one. This is a reversible process.
Sum frequency generation spectroscopy, SFG, was used for the surface characterization at the gas-liquid interface of the 1-butyl-3-methylimidazolium cation combined with the following anions: Br-, I-, PF6-, BF4-, (CF3SO2)2N- (imide), SCN-, CH3SO3- (MeSO3), CH3SO4- (MS), and (CN)2N- (DCN). The SFG spectra obtained for the different ionic liquids were similar independent of the anion selected; therefore, a comprehensive analysis for the surface characterization of the ionic liquids' cation was focused only on the PF6- and Br- anion combinations. For an accurate identification of the vibrational modes observed, FT-IR and Raman spectroscopy in combination with isotopic labeling with deuterium and polarized Raman spectroscopy was used. The cation orientation was determined by analysis of polarization-dependent SFG spectra. For a compound dried in a vacuum to < or = 2 x 10(-5) Torr, the cation appears to be oriented with the ring laying flat along the surface plane and the butyl chain projecting into the gas phase independent of the anion identity.
Sum frequency generation vibrational spectroscopy was used to determine the orientation of the cations in a room-temperature ionic liquid at the air-liquid interface. The ionic liquid that was studied was 1-butyl-3methylimidazolium bis-trifluoromethylsulfonimide, [BMIM] + [imide] -. The orientation of the cation, [BMIM] + , was studied as a function of water pressure in the vapor over the range of 10 -5 to 200 Torr. At water pressures below 10 -4 Torr, the imidazolium ring was oriented parallel to the surface plane. On increasing the water pressure to greater than 10 -4 Torr, the imidazolium ring tipped up from the surface with an angle along the surface normal of 40-55°. No water signal was observed in the spectra obtained at the water pressures studied here.
The arrangement of ions at the platinum electrode in the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate has been determined using sum frequency generation vibrational spectroscopy (SFG), electrochemical impedance spectroscopy (EIS), and the vibrational Stark effect. The results indicate that CO adsorbed on the Pt electrode has a Stark shift of 30-35 cm(-1)/V in the ionic liquid. The potential of zero charge (PZC) of the ionic liquid-Pt system is approximately -500 mV (vs Ag wire), with a capacitance of 0.12 F/m2. Further, polarization-dependent SFG experiments suggest the ions reorganize at the surface depending on the electrode charge. In combination, all these results indicate that the ions of a neat ionic liquid are organized in a Helmholtz layer at the electrified metal electrode interface.
Microscopic understanding of interaction between H2O and MAPbI3 (CH3NH3PbI3) is essential to further improve efficiency and stability of perovskite solar cells. A complete picture of perovskite from initial physical uptake of water molecules to final chemical transition to its monohydrate MAPbI3·H2O is obtained with in situ infrared spectroscopy, mass monitoring, and X-ray diffraction. Despite strong affinity of MA to water, MAPbI3 absorbs almost no water from ambient air. Water molecules penetrate the perovskite lattice and share the space with MA up to one H2O per MA at high-humidity levels. However, the interaction between MA and H2O through hydrogen bonding is not established until the phase transition to monohydrate where H2O and MA are locked to each other. This lack of interaction in water-infiltrated perovskite is a result of dynamic orientational disorder imposed by tetragonal lattice symmetry. The apparent inertness of H2O along with high stability of perovskite in an ambient environment provides a solid foundation for its long-term application in solar cells and optoelectronic devices.
The purpose of this investigation is to study the ionic liquid/quartz interface with sum frequency generation vibrational spectroscopy (SFG). SFG spectroscopy was chosen for this study because of its unique ability to yield vibrational spectra of molecules at an interface. Different polarization combinations are used, which probe different susceptibilities, giving SFG the ability to determine molecular orientation at the interface. The ionic liquids used were 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF(4)], and 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)]. To determine the influence of the molecular structure and charge on orientation at the interface, neutral, 1-methylimidazole, and 1-butylimidazole were also studied. Raman spectra and depolarization ratios were obtained for neat samples of 1-methylimidazole, 1-butylimidazole, and 1-butyl-3-methylimidazolium tetrafluoroborate recorded from 2700 to 3300 cm(-1). SFG spectra of the 1-methylimidazole/quartz interface showed both methyl and aromatic C-H vibrations. Orientation calculations determined that the ring of the molecule is tilted 45-68 degrees from normal, with the methyl group oriented 32-35 degrees from normal. The SFG spectra of 1-butylimidazole contain several resonances from the alkyl chain with only one weak resonance from the aromatic ring. Orientation calculations suggest that the ring is lying in the plane of the surface with the methyl group pointing 43-47 degrees from normal. The orientation of the [BMIM][PF(6)] ionic liquid was sensitive to trace amounts of water and had to be evacuated to <3 x 10(-5) Torr for the water to be removed. SFG spectra of both ionic liquids were similar, displaying resonances from the alkyl chain as well as the aromatic ring. Orientation analysis suggests the aromatic ring was tilted 45-90 degrees from normal for [BMIM][BF(4)], while the ring for [BMIM][PF(6)] was tilted 38-58 degrees from normal. This suggests the orientation of the molecule is influenced by the size of the anion.
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