Directing the Selectivity of CO Electrolysis to Acetate by Constructing Metal-Organic Interfaces.

Electrochemically converting CO2 to valuable chemicals holds great promise for closing the anthropogenic carbon cycle. Owing to complex reaction pathways and shared rate-determining steps, directing the selectivity of CO2 /CO electrolysis to a specific multicarbon product is very challenging. We report here a strategy for highly selective production of acetate from CO electrolysis by constructing metal-organic interfaces. We demonstrate that the Cu-organic interfaces constructed by in situ reconstruction of Cu complexes show very impressive acetate selectivity, with a high Faradaic efficiency of 84.2 % and a carbon selectivity of 92.1 % for acetate production, in an alkaline membrane electrode assembly electrolyzer. The maximum acetate partial current density and acetate yield reach as high as 605 mA cm-2 and 63.4 %, respectively. Thorough structural characterizations, control experiments, operando Raman spectroscopy measurements, and density functional theory calculation results indicate that the Cu-organic interface creates a favorable reaction microenvironment that enhances *CO adsorption, lowers the energy barrier for C-C coupling, and facilitates the formation of CH3 COOH over other multicarbon products, thus rationalizing the selective acetate production.

Au(100) as a Template for Pentacene Monolayer.

The surface of quasi-hexagonal reconstructed Au(100) is used as the template for monolayer pentacene (PEN) self-assembly. The system is characterized by means of scanning tunneling microscopy at room temperature and under an ultra-high vacuum. A new modulated pattern of molecules with long molecular axes (MA) arranged along hex stripes is found. The characteristic features of the hex reconstruction are preserved herein. The assembly with MA across the hex rows leads to an unmodulated structure, where the molecular layer does not recreate the buckled hex phase. The presence of the molecules partly lifts the reconstruction-i.e., the gold hex phase is transformed into a (1×1) phase. The arrangement of PEN on the gold (1×1) structure is the same as that of the surrounding molecular domain on the reconstructed surface. The apparent height difference between phases allows for the distinction of the state of the underlying gold surface.

Non-Conjugated Poly(Diphenylene Phthalide)-New Electroactive Material.

In organic electronics, conjugated conductive polymers are most widely used. The scope of their application is currently very wide. Non-conjugated polymers are used much less in electronics and are usually used as insulation materials or materials for capacitors. However, the potential of non-conjugated polymers is much wider, due to the fact that new electronic materials with unique electronic properties can be created on the basis of non-conjugated polymers, as well as other inorganic dielectrics. This article demonstrates the possibilities of creating electrically conductive materials with unique electronic parameters based on non-conjugated polymers. The results of the study of the sensory properties of humidity are given as examples of the practical application of the structure. The abnormal electronic properties are realized along the interface of two polymer dielectrics with functional polar groups. The submicron films of polydiphenylenephthalide were used as a dielectric. It is shown that a quasi-two-dimensional electronic structure with abnormally large values of conductivity and mobility of charge carriers occurs along the interface. These structures are often called quasi-two-dimensional electron gas (Q2DEG). This article describes the manufacturing processes of multielectrode devices. Polymer films are deposited via the spin-coating method with polymer solutions in cyclohexanone. The metal electrodes were manufactured through thermal deposition in a vacuum. Three types of metal electrodes made of aluminum, copper and chromium were used. The influence of the electron work function of contacting metals on the electronic parameters of the structure was studied. It was established that the work function decrease leads to an increase in the conductivity and mobility of charge carriers. The charge carrier parameters were estimated based on the analysis of the current-voltage characteristics within the space-charge-limited current technique. The Richardson-Schottky thermionic emission model was used to evaluate values a potential barrier at metal/organic interfaces. It was established that the change in ambient humidity strongly affects the electronic transport properties along the polymer/polymer interface. It is demonstrated that the increase in conductivity with an increase in humidity occurs due to an increase in the mobility of charge carriers and a decrease in the height of the potential barrier at the three-dimensional metal contact with two-dimensional polymer interface. The potential barrier between the electrode and the bulk of the polymer film is significantly higher than between the electrode and the quasi-two-dimensional polymer structure.

Exciton Modulation in Perylene-Based Molecular Crystals Upon Formation of a Metal-Organic Interface From Many-Body Perturbation Theory.

Excited-state processes at organic-inorganic interfaces consisting of molecular crystals are essential in energy conversion applications. While advances in experimental methods allow direct observation and detection of exciton transfer across such junctions, a detailed understanding of the underlying excitonic properties due to crystal packing and interface structure is still largely lacking. In this work, we use many-body perturbation theory to study structure-property relations of excitons in molecular crystals upon adsorption on a gold surface. We explore the case of the experimentally-studied octyl perylene diimide (C8-PDI) as a prototypical system, and use the GW and Bethe-Salpeter equation (BSE) approach to quantify the change in quasiparticle and exciton properties due to intermolecular and substrate screening. Our findings provide a close inspection of both local and environmental structural effects dominating the excitation energies and the exciton binding and nature, as well as their modulation upon the metal-organic interface composition.

Strain Effects on the Energy-Level Alignment at Metal/Organic Semiconductor Interfaces.

Flexible and wearable devices are among the upcoming trends in the opto-electronics market. Nevertheless, bendable devices should ensure the same efficiency and stability as their rigid analogs. It is well-known that the energy barriers between the metal Fermi energy and the molecular levels of organic semiconductors devoted to charge transport are key parameters in the performance of organic-based electronic devices. Therefore, it is paramount to understand how the energy barriers at metal/organic semiconductor interfaces change with bending. In this work, we experimentally measure the interface energy barriers between a metallic contact and small semiconducting molecules. The measurements are performed in operative conditions, while the samples are bent by a controlled applied mechanical strain. We determine that energy barriers are not sensitive to bending of the sample, but we observe that the hopping transport of the charges in flat molecules can be tuned by mechanical strain. The theoretical model developed for this work confirms our experimental observations.

Energy-Level Alignment of a Hole-Transport Organic Layer and ITO: Toward Applications for Organic Electronic Devices.

2,2',6,6'-Tetraphenyl-4,4'-dipyranylidene (DIPO-Ph4) was grown by vacuum deposition on an indium tin oxide (ITO) substrate. The films were characterized by atomic force microscopy as well as synchrotron radiation UV and X-ray photoelectron spectroscopy to gain an insight into the material growth and to better understand the electronic properties of the ITO/DIPO-Ph4 interface. To interpret our spectroscopic data, we consider the formation of cationic DIPO-Ph4 at the ITO interface owing to a charge transfer from the organic layer to the substrate. Ionization energy DFT calculations of the neutral and cationic species substantiate this hypothesis. Finally, we present the energetic diagram of the ITO/DIPO-Ph4 system, and we discuss the application of this interface in various technologically relevant systems, as a hole-injector in OLEDs or as a hole-collector interfacial layer adjacent to the prototypical OPV layer P3HT:PCBM.