In solid catalysts with ionic liquid layers (SCILLs), ionic liquid (IL) thin films are used to modify the activity and selectivity of catalytic materials. In this work, we investigated the adsorption behavior of the IL 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C2C1Im][NTf2] on Pt(111) by combining experimental and theoretical studies. Under ultrahigh vacuum (UHV) conditions, the IL was deposited onto a Pt(111) single crystal surface by physical vapor deposition (PVD) at different surface temperatures (200, 300, and 400 K). The adsorption process was monitored by in situ infrared reflection absorption spectroscopy (IRAS). Complementary to the IRAS studies, we performed density functional theory (DFT) calculations and analyzed the adsorption motifs and orientation of the IL ions. In total, we calculated four different systems: (a) [C2C1Im]+ and [NTf2]- ions in the gas phase; [NTf2]- anions in (b) small (4 × 4) and (c) large (6 × 6) Pt(111) supercells; and (d) a complete ion pair of [C2C1Im][NTf2] in a (6 × 6) Pt(111) supercell. Based on DFT, we simulated IR spectra and compared them to the experimental data. Our results suggest that the binding motif and orientation of the IL is strongly dependent on the actual IL coverage. In the monolayer (ML), [NTf2]- interacts strongly with the metal surface and adopts a specific orientation in which it interacts with the Pt surface via the SO2 groups. Also the [C2C1Im]+ cations adopt a preferential orientation up to coverages of 1 ML. Upon transition to the multilayer region, the specific orientation of the ions is gradually lost.
We used temperature-programmed infrared reflection absorption spectroscopy (TP-IRAS) to study the desorption behavior of CO on Pt(111) coadsorbed with four kinds of ionic liquids (ILs), namely 1-butyl-1-methyl-pyrrolidinium-bis(trifluoromethylsulfonyl)imide ([C4C1Pyr][NTf2]), 1-ethyl-3-methyl-imidazolium-bis(trifluoromethylsulfonyl)imide ([C2C1Im][NTf2]), 1-butyl-1-methyl-pyrrolidinium-trifluoro-methanesulfonate ([C4C1Pyr][OTf]), and 1-butyl-1-methyl-pyrrolidinium-hexafluorophosphate ([C4C1Pyr][PF6]). We found that CO desorbs earlier from a Pt(111) surface with coadsorbed ILs than without. In addition, the CO desorption temperature varies between different types of coadsorbed ILs, which follows the order: [C4C1Pyr][PF6] (365 K) > [C4C1Pyr][NTf2] (362 K) > [C2C1Im][NTf2] (352 K) > [C4C1Pyr][OTf] (348 K). We ascribe the difference in CO desorption temperature to the different interaction strength between ILs and the Pt(111) surface. A stronger IL-Pt(111) interaction leads to a lower CO desorption temperature. We suggest that TP-IRAS experiments of CO coadsorbed with ILs can be a useful method to aid the characterization of the interaction strength between ILs and metal surfaces such as Pt(111).
Employing molecular photoswitches, we can combine solar energy conversion, storage, and release in an extremely simple single molecule system. In order to release the stored energy as electricity, the photoswitch has to interact with a semiconducting electrode surface. In this work, we explore a solar-energy-storing model system, consisting of a molecular photoswitch anchored to an atomically defined oxide surface in a liquid electrolyte and under potential control. Previously, this model system has been proven to be operational under ultrahigh vacuum (UHV) conditions. We used the tailor-made norbornadiene derivative 2-cyano-3-(4-carboxyphenyl)norbornadiene (CNBD) and characterized its photochemical and electrochemical properties in an organic electrolyte. Next, we assembled a monolayer of CNBD on a well-ordered Co3O4(111) surface by physical vapor deposition in UHV. This model interface was then transferred into the liquid electrolyte and investigated by photoelectrochemical infrared reflection absorption spectroscopy experiments. We demonstrate that the anchored monolayer of CNBD can be converted photochemically to its energy-rich counterpart 2-cyano-3-(4-carboxyphenyl)quadricyclane (CQC) under potential control. However, the reconversion potential of anchored CQC overlaps with the oxidation and decomposition potential of CNBD, which limits the electrochemically triggered reconversion.
In this work, we investigated the interaction of phenylphosphonic acid (PPA, C6H5PO3H2) with atomically-defined Co3O4(111) thin films, grown on Ir(100), under ultrahigh vacuum (UHV) conditions and in the electrochemical environment. In the first step, we employed infrared reflection absorption spectroscopy (IRAS) and followed the formation of a saturated monolayer (380 K) in UHV. We observed that the binding motif changes from a chelating tridentate in the sub-monolayer regime to a chelating bidentate at full monolayer coverages. In the electrochemical environment, we analyzed the interaction of PPA with the same Co3O4(111) surface by electrochemical infrared reflection absorption spectroscopy (EC-IRRAS) (0.3 VRHE-1.3 VRHE). When adsorbed at pH 10 from an ammonia buffered aqueous solution, PPA binds to the surface in form of a fully deprotonated chelating bidentate. With increasing electrode potential, we observed two fully reversible processes. At low buffer concentration, protons are released upon oxidation of surface Co2+ ions and lead to protonation of the anchored phosphonates. At high buffer concentration, most of the protons released are accepted by NH3. Simultaneously, the surface phosphonate changes its adsorption motif from bidentate to tridentate while adopting a more upright geometry.
Molecular photoswitches provide an extremely simple solution for solar energy conversion and storage. To convert stored energy to electricity, however, the photoswitch has to be coupled to a semiconducting electrode. In this work, we report on the assembly of an operational solar-energy-storing organic-oxide hybrid interface, which consists of a tailor-made molecular photoswitch and an atomically-defined semiconducting oxide film. The synthesized norbornadiene derivative 2-cyano-3-(4-carboxyphenyl)norbornadiene (CNBD) was anchored to a well-ordered Co3O4(111) surface by physical vapor deposition in ultrahigh vacuum. Using a photochemical infrared reflection absorption spectroscopy experiment, we demonstrate that the anchored CNBD monolayer remains operational, i.e., can be photo-converted to its energy-rich counterpart 2-cyano-3-(4-carboxyphenyl)quadricyclane (CQC). We show that the activation barrier for energy release remains unaffected by the anchoring reaction and the anchored photoswitch can be charged and discharged with high reversibility. Our atomically-defined solar-energy-storing model interface enables detailed studies of energy conversion processes at organic/oxide hybrid interfaces.
Photochemical in situ studies in a well-controlled surface science environment can help to understand photochemical reactions in organic thin films in more detail. To perform such studies without external focusing or light guiding systems, we designed a high-intensity UV-photon source, which is compatible with an ultra-high vacuum (UHV) environment. The UV source is based on a high power light-emitting diode (LED), soldered onto a copper heat reservoir to avoid overheating. The LED can be placed in close vicinity in front of a single crystal, providing flux densities of 2 × 1018 photons s-1 cm-2 at a wavelength of 365 nm. Thus, the device provides light intensities one order of magnitude higher as compared to conventional continuous wave arc lamps, at only a small variation of the flux of less than ±20% over a sample surface of 10 × 8 mm2. The UV source is mounted in a UHV infrared reflection absorption spectroscopy system and triggered by using the IR spectrometer. This allows fully automatized in situ IR studies of photochemical reactions at interfaces and thin films. We prove the functionality of the device by studying the photochemical conversion of norbornadiene (NBD) to quadricyclane (QC) mediated by the photosensitizer 4,4'-bis(dimethylamino)benzophenone (Michler's ketone, MK). NBD and MK were grown by physical vapor deposition in the form of thin films on Pt(111) at 120 K. Even at prolonged UV irradiation (>100 s), the temperature of the sample increased by less than 10 K. We report first successful conversion of NBD to QC under UHV conditions and follow the conversion behavior as a function of the photon dose and NBD/MK ratio. Initial quantum yields of up to 23% and selectivity for a QC of 70% are obtained at NBD/MK of 7.4:1, indicating good electronic coupling between NBD and MK even in a frozen multilayer. For both very small and very large NBD loadings, the conversion efficiency decreases, which is attributed to the effect of the metallic substrate and phase separation in thick multilayers, respectively.
We have studied the anchoring mechanism of a phosphonic acid on an atomically defined oxide surface. Using time-resolved infrared reflection absorption spectroscopy, we investigated the reaction of deuterated phenylphosphonic acid (DPPA, C6H5PO3D2) with an atomically defined Co3O4(111) surface in situ during film growth by physical vapor deposition. We show that the binding motif of the phosphonate anchor group changes as a function of coverage. At low coverage, DPPA binds in the form of a chelating tridentate phosphonate, while a transition to a chelating bidentate occurs close to monolayer saturation coverage. However, the coverage-dependent change in the binding motif is not associated with a major change of the molecular orientation, suggesting that the rigid phosphonate linker always maintains the DPPA in a strongly tilted orientation irrespective of the surface coverage.
