Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Scanning tunnelling microscopy (STM) enables us to directly observe the dynamic behaviour of organic molecules on surfaces. While imaging atoms and molecules using STM is certainly fascinating by itself, corresponding temperature-dependent measurements allow for the quantitative determination of the energetics and kinetics of the underlying molecular surface processes. Herein, we review recent advances in the STM investigation of the dynamic behaviour of adsorbed porphyrins at and close to room temperature. Three different case studies are discussed, providing insight into the dynamics of diffusion, rotation, reaction, and molecular switching at surfaces, based on isothermal STM measurements. The reviewed examples demonstrate that variable temperature STM can be a suitable tool to directly monitor the dynamic behaviour of individual adsorbed molecules, at and close to room temperature. Free base porphyrins on Cu(111) proved to be particularly suitable for these studies due to the strong bonding interaction between the iminic nitrogen atoms in the porphyrin macrocycle and the Cu substrate atoms. As a consequence, the corresponding activation energies for surface diffusion, self-metalation reaction and conformational switching are of a magnitude that allows for monitoring the processes at and around room temperature, in contrast to most previous studies, which were performed at cryogenic temperatures. The kinetic analysis of the surface diffusion and self-metalation was performed using an Arrhenius approach, yielding the corresponding activation energies and preexponential factors. In contrast, the conformational switching process was analysed in the framework of transition state theory, based on the Eyring equation. This approach provides a more detailed insight into interpretable thermodynamic potentials, i.e., the enthalpic and entropic contributions to the activation barrier. The analysis shows that at room temperature the adsorption and switching behaviour of the investigated free base porphyrin on Cu(111) is dominated by entropic effects. Since the entropic energy contribution vanishes at low temperatures, the importance of experiments conducted at temperatures close to room temperature is emphasized

General and selective deoxygenation by hydrogen using a reusable earth-abundant metal catalyst

Chemoselective deoxygenation by hydrogen is particularly challenging but crucial for an efficient late-stage modification of functionality-laden fine chemicals, natural products, or pharmaceuticals and the economic upgrading of biomass-derived molecules into fuels and chemicals. We report here on a reusable earth-abundant metal catalyst that permits highly chemoselective deoxygenation using inexpensive hydrogen gas. Primary, secondary, and tertiary alcohols as well as alkyl and aryl ketones and aldehydes can be selectively deoxygenated, even when part of complex natural products, pharmaceuticals, or biomass-derived platform molecules. The catalyst tolerates many functional groups including hydrogenation-sensitive examples. It is efficient, easy to handle, and conveniently synthesized from a specific bimetallic coordination compound and commercially available charcoal. Selective, sustainable, and cost-efficient deoxygenation under industrially viable conditions seems feasible. © 2019 The Authors

Switching adsorption and growth behavior of ultrathin [C2C1Im][OTf] films on Au(111) by Pd deposition

Combining in vacuo deposition of ultrathin ionic liquid (UTIL) films with angle-resolved X-ray photoelectron spectroscopy (ARXPS), we demonstrate that by deposition of submonolayer amounts of Pd onto Au(111) the initial growth mode of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([C2C1Im][OTf]) can be switched from three-dimensional (3D) to two-dimensional (2D) growth, that is, from non-wetting to wetting. On clean Au(111), pronounced 3D growth occurs on top of an initially formed 2D wetting layer with cations and anions next to each other in a checkerboard arrangement. After pre- or postdeposition of only 0.7 ML Pd, two-dimensional layer-by-layer growth is found, which is attributed to strong attractive interactions between [C2C1Im][OTf] and surface Pd. For Pd post deposition onto the IL, the ARXPS data revealed particularly strong interactions between the dialkylimidazolium cation and Pd atoms, which considerably reduce the regular surface alloying of Pd with the Au substrate stabilizing Pd at the metal surface. In the context of heterogeneous catalysis using the SCILL (solid catalyst coated with ionic liquid layer) concept, these results directly provide a possible explanation on the molecular level for the beneficial influence of the IL layer in case of heterogeneous metal alloy catalysts

Magnetotransport properties of iron microwires fabricated by focused electron beam induced autocatalytic growth

We have prepared iron microwires in a combination of focused electron beam induced deposition (FEBID) and autocatalytic growth from the iron pentacarbonyl, Fe(CO)5, precursor gas under UHV conditions. The electrical transport properties of the microwires were investigated and it was found that the temperature dependence of the longitudinal resistivity (rhoxx) shows a typical metallic behaviour with a room temperature value of about 88 micro{\Omega} cm. In order to investigate the magnetotransport properties we have measured the isothermal Hall-resistivities in the range between 4.2 K and 260 K. From these measurements positive values for the ordinary and the anomalous Hall coefficients were derived. The relation between anomalous Hall resistivity (rhoAN) and longitudinal resistivity is quadratic, rhoAN rho^2 xx, revealing an intrinsic origin of the anomalous Hall effect. Finally, at low temperature in the transversal geometry a negative magnetoresistance of about 0.2 % was measured

Activated adsorption of methane on Pt(1 1 1) —an in situ XPS study

We have investigated the activated adsorption of methane on Pt(1 1 1) by the combination of a supersonic molecular beam and in situ high-resolution X-ray photoelectron spectroscopy at the German synchrotron radiation facility BESSY II. On exposing the surface to a methane beam with kinetic energies between 0.30 and 0.83 eV, CH3 is formed as a stable species at 120 K; upon heating, at around 260 K the adsorbed methyl partly dehydrogenates to CH and partly recombines to methane, which desorbs. Upon adsorption at 300 K, CH is directly formed as a stable surface species. To verify the chemical identity of CH as an intermediate, we have also investigated the thermal evolution of a saturated ethylene layer. Upon heating, at ∼290 K partial ethylene desorption and the formation of ethylidyne is clearly observed in the spectra, as expected from the literature. From the binding energies and also from the vibrational signature of the C 1s spectra, an unequivocal assignment of the various surface species is possible. Measurements of the sticking coefficients of methane show that the saturation coverage at 120 K depends on the kinetic energy of the molecule; furthermore, the sticking coefficient for vibrationally excited molecules is strongly enhanced

The band structure of BeTe - a combined experimental and theoretical study

Using angle-resolved synchrotron-radiation photoemission spectroscopy we have determined the dispersion of the valence bands of BeTe(100) along $\Gamma X$, i.e. the [100] direction. The measurements are analyzed with the aid of a first-principles calculation of the BeTe bulk band structure as well as of the photoemission peaks as given by the momentum conserving bulk transitions. Taking the calculated unoccupied bands as final states of the photoemission process, we obtain an excellent agreement between experimental and calculated spectra and a clear interpretation of almost all measured bands. In contrast, the free electron approximation for the final states fails to describe the BeTe bulk band structure along $\Gamma X$ properly.Comment: 21 pages plus 4 figure

Probing the interaction of Rh, Co and bimetallic Rh–Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation

The interaction of CeO2-supported Rh, Co and bimetallic Rh–Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1–5%), Rh forms 2–8 nm particles. Between 473–673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt

Massive conformational changes during thermally induced self-metalation of 2H-tetrakis-(3,5-di-tert-butyl)-phenylporphyrin on Cu(111)

Based on a combined scanning tunnelling microscopy and X-ray photoelectron spectroscopy study we present detailed insights into pronounced changes of long-range order and intramolecular conformation during the self-metalation of 2H-5,10,15,20-tetrakis-(3,5-di-tert-butyl)-phenylporphyrin (2HTTBPP) to CuTTBPP on Cu(111). Upon metalation, the porphyrin literally “pops up” from the surface, due to a drastically reduced molecule–substrate interaction

Industrially scalable and cost-effective Mn2+ doped ZnxCd1−xS/ZnS nanocrystals with 70% photoluminescence quantum yield, as efficient down-shifting materials in photovoltaics

We present colloidally stable and highly luminescent ZnxCd1−xS:Mn/ZnS core–shell nanocrystals (NCs) synthesized via a simple non-injection one-pot, two-step synthetic route, which can be easily upscaled. A systematic variation of the reaction component, parameters and thickness of the ZnS shell yielded doped nanocrystals with a very high photoluminescence quantum yield (Φpl) of 70%, which is the highest value yet reported for these Mn-doped sulfide-semiconductor NCs. These materials can be synthesized with high reproducibility in large quantities of the same high quality, i.e., the same Φpl using accordingly optimized reaction conditions. The application of these zero-reabsorption high quality NCs in the light conversion layers, deposited on top of a commercial monocrystalline silicon (mono-Si) solar cell, led to a significant enhancement of the external quantum efficiency (EQE) of this device in the ultraviolet spectral region between 300 and 400 nm up to ca. 12%. EQE enhancement is reflected by an increase in the power conversion efficiency (PCE) by nearly 0.5 percentage points and approached the theoretical limit (0.6%) expected from down-shifting for this Si solar cell. The resulting PCE may result in a BoM (bill of materials) cost reduction of app. 3% for mono-Si photovoltaic modules. Such small but distinct improvements are expected to pave the road for an industrial application of doped semiconductor NCs as cost-effective light converters for silicon photovoltaic (PV) and other optoelectronic applications