Projects

So far, materials are seen as passive items. This project aims at providing a solution that can turn objects into matter that can perceive and communicate trigger events. If materials are turned capable of reporting their encountered history, this will significantly contribute to i) ensuring product safety and reliability, ii) making predictive maintenance possible, iii) making complex recycling fates of materials transparent, and iv) enabling autonomous, robot-controlled, resilient manufacturing (Industry 4.0).

The key to realize this vision is to make use of smart magnetic particles, largely based on iron oxide (SmartRust). To achieve SmartRust, micron-sized (1-10 µm) supraparticles are composed of magnetic nano building blocks, the “signal transducers”, which are combined with other non-magnetic moieties, the “sensitizers”. A toolbox-like approach using spray-drying allows for nanoparticle assembly of a transducer and a sensitizer type of choice to specifically target a desired type of stimulus. The SmartRust particles are then integrated in materials` matrices.

It is hypothesized – and yet an open research question! - that there is an interplay of two magnetic interaction principles: on a hierarchical level I, a trigger event will alter the intra-supraparticle magnetic interactions of the nanoparticles within individual supraparticles. On a hierarchical level II, a trigger event will alter the inter-supraparticle magnetic interactions among the supraparticles when the matrix of the materials, where the supraparticles are embedded in, is altered.

The scientific idea is that this magnetic interaction information can be read out fast, easily, in a non-destructive way and from within a material, enabled by the technique magnetic particle spectroscopy (MPS).

If this endeavour is successful in obtaining a meaningful signal-structure-trigger correlation, ultimately, design rules could be deduced how to create conscious matter using SmartRust.

Therapeuticoptions for Cystic Fibrosis (CF), the most common genetic metabolic disease inEurope, are insufficient. We propose a novel therapeutic strategy that obviatesthe need to overcome the human epithelial airway barrier by directly addressingthe bacterial infections that cause respiratory failure and high CF patientmortality. Namely, an inhalable application of antisense oligomers (ASOs) targetingselectively the chronic microbial pulmonary CF lung infections. To create abasis for this new ASO-based CF therapy approach we will design and synthesize potentand type selective ASOs, define their physiological and resistance effects andfurther explore the targeted transport and release when formulated as modularsystems.

G-protein coupled receptors (GPCRs) are membrane proteins that are excellent targets for drugs. Approximately 30% of the approved drugs and currently developed drug candidates address G-protein coupled receptors. Orexin OX1 receptors, which belong to Class A GPCRs, are also regarded as highly interesting pharmaceutical targets. OX1 receptors are expressed in the central nervous system and are involved in eating disorders, addiction and pain processing. Furthermore, due to their expression on colon tumor cells, OX1 receptors are in principle suitable for the development of receptor-mediated endoradiotherapy of these peripheral tumors. The project deals with the interdisciplinary development of subtype-selective radioligands for OX1 receptors. These will be used for PET imaging in the CNS and developed as radioligands that can reach peripheral tumors and are suitable for radiotherapy. The project will be based on our new OX1R-selective antagonist JH112, which we have synthesized and in-vitro pharmacologically investigated. In an interaction of medical chemistry and radiochemistry/molecular imaging, chemical modifications and functionalizations will be performed with the aim of developing radioligands with high affinity and selectivity, whose physicochemical and pharmacokinetic properties are optimal for imaging. The design of the new ligands is structure-based. We use a high-resolution X-ray crystal structure of our lead compound JH112 in complex with the OX1 receptor. The resulting structural insights enable us to design the new radioligands efficiently and rationally.

The central focus of SOLAREC project is the creation of plasmonic Schottky junctions, M/(Pd or Au)CN as monometallic functional binary nanomaterials. How? By synthesizing gold and palladium nanoparticles (NPs) with 2 to 10 nm size to exploit their quantum effect and plasmonic properties, like hot electron injection, co-catalytic functions, and electron trap site functionalities. To maximize such metal NPs’ functionalities, its fundamental to ensure close interaction with a visible-light absorber. For that purpose, carbon nitrides will be used as visible absorber and support material thanks to its appealing medium band gap of 2.7 eV, structural pores (making it an excellent host of antennae moieties), and amine-rich surface chemistry.

Project M03 will perform molecular dynamics simulations for the in-depth understanding of effects that occur at the nanometre scale such as the self-organisation of IL layers and films (Kawska-Zahn approach). To account for charge polarisation in metal droplets and nanoparticles, the MM models will be extended by QeQ approaches. This effectively expands QM characterisation to MD simulations reaching the million atoms scale. Using multi-state MM models triggered by QM/MM calculations, the relaxation dynamics of deactivation and self-healing reactions of the catalyst will be elucidated.

The project aims at a microscopic quantum mechanical description of catalytic materials and processes in the three Areas A, B, and C (SCALMS, Interface-enhanced SILP, and Advanced SCILL). We will interpret and explain experimental data and develop and suggest strategies to optimise catalytic materials and processes. Based on conventional and newly developed density-functional methods (i) ab initio molecular dynamics simulations will be performed and (ii) slab and cluster models as well as (iii) molecular systems will be studied. Detailed atomistic information on catalytic sites, reaction steps, and diffusion and segregation processes as well as input for other theory projects in Area M will be provided.

In Project C05, we will explore the potential of Advanced SCILLs in electrocatalytic hydrogenation. Using a broad range of EC in situ spectroscopies, microscopies, and advanced EC characterisation methods, we will scrutinise the selective hydrogenation of unsaturated ketones and nitriles on a broad range of test electrodes (single crys-tals, atomically defined model electrodes, complex alloys and supported nanoalloys). At the electrified interface, we will explore (i) how ILs interact with specific sites at the electrode, (ii) how ILs interact with reactants during the electrocatalytic reaction, (iii) how these interactions affect the mechanism and kinetics, and (iv) how ILs can be tailored to enhance the selectivity of electrohydrogenation.

In Project C03, we will elucidate the fundamental interaction mechanisms between functionalised ILs and catalytically active surfaces and their role in catalytic hydrogenation. To this aim, we will combine in situ studies at single crystals and atomically defined model catalysts in UHV with operando spectroscopy on real SCILLs under true working conditions. Our key tools will be vibrational spectroscopy (IRAS, PM-IRAS, DRIFTS) in combination with online analytics of products (MB experiments, TPD, TPR, online GC, online QMS). Specifically, we will identify interaction mechanisms at the surface, the orientation of IL ions, conformational changes, specific interactions with co-adsorbates, reaction intermediates and selectivity patterns.

We aim at understanding the fundamental processes and the chemical/morphological stability of IL/solid interfaces in Advanced SCILLs. We will proceed in three steps: for non-functionalised and functionalised ILs, we will investigate (a) the chemical interaction and the wetting behaviour of (ultra)thin IL films on the supporting solid on a wide range of well-defined substrates, (b) the stability of Advanced SCILL systems from the point of view of interface chemistry and morphology, and finally, (c) strategies to control and to switch the adsorption and wetting behaviour. Using ARXPS, STM, and AFM, we will extract interface compositions, depth profiles, chemical states, adsorption geometries and growth behaviour.

We aim at understanding the fundamental processes that determine the properties of the gas/liquid interface of Interface-enhanced SILPs. Towards this aim, the Steinrück and Koller groups will apply X-ray photoelectron spectroscopy under ultraclean conditions and the pendant drop method as well as surface light scattering under reac-tion conditions. This enables to develop relationships between the surface properties on the nanometre scale and the macroscopic properties surface tension, viscosity and dynamics of surface fluctuations. Based on this concerted characterisation, we envisage to identify those factors which are responsible for the enrichment of catalytic metal complexes at IL interfaces.

Project B01 focuses on the design and synthesis of functionalised and task-specific ILs, with the aim (i) to tailor support/IL interfaces and (ii) to develop electrocatalytically active interface-enhanced SILPs. The latter concept will combine catalytic functionalities operating at both the gas/IL and the IL/solid interfaces for the electrochemical production of hydrogen from water (or protons) and the hydrogenation of divers C=C and C=O moieties in selected substrates. These two processes shall be controlled by the incorporation of identical task-specific structural motifs in the IL and in the active transition metal catalyst. The long-term objective will be the direct electrocatalytic hydrogenation of substrates in a ‘tandem-like’ system.

A06 focuses on the technical dimension of SCALMS by exploring quantitatively the expected enhanced poisoning resistance and stability in dehydrogenation catalysis. For the specific case of isobutane dehydrogenation, we will perform systematic poisoning experiments under surface science and technical conditions. The data will be compared to traditional catalysts. Spectroscopic and reaction engineering studies will be applied to determine the concentration, reactivity, and regenerability of active sites of the SCALMS systems after contact with defined amounts of traditional poisons or after exposure to conditions favouring coke formation. We will also investigate ternary SCALMS to elucidate the effect of further alloying and dissolution on the adsorption strengths, reactivity, and stability.

A01 aims at understanding the catalytic properties of SCALMS and the dynamic behaviour of the active sites at the gas/liquid interface to enable their knowledge-based improvement. We will study model and real-world cata-lysts in UHV and near-ambient pressure to technical operating conditions. Towards providing a full “depth-resolved” picture, we will employ laboratory- and synchrotron-based X-ray spectroscopic techniques with specific surface or bulk sensitivity. The fundamental studies will reveal details such as the metal distribution in the liquid alloy, its (de-)wetting behaviour on supports, its electronic structure, as well as its behaviour and surface chemistry as a function of temperature and pressure.

We aim at understanding the fundamental processes that determine the properties of the gas/liquid interface of Interface-enhanced SILPs. Towards this aim, the Steinrück and Koller groups will apply X-ray photoelectron spectroscopy under ultraclean conditions and the pendant drop method as well as surface light scattering under reaction conditions. This enables to develop relationships between the surface properties on the nanometre scale and the macroscopic properties surface tension, viscosity and dynamics of surface fluctuations. Based on this concerted characterisation, we envisage to identify those factors which are responsible for the enrichment of catalytic metal complexes at IL interfaces

The abrasion and fracture toughness of polymers can considerably be increased by adding hard nanoparticles such as silica. This is mainly caused by the development of localized shear bands, initiated by the stress concentrations stemming from the inhomogeneity of the composites. Other mechanisms responsible for toughening are debonding of the particles and void growth in the polymer matrix. Both phenomena strongly depend on the structure and chemistry of the polymers and shall be explored for branched networks (epoxy) and matrices of nestled fibres (cellulose, aramid).

The goal of the present project is to develop and apply dynamics simulation approaches to understanding polymer-nanoparticle and polymer-polymer interactions at i) the atomic scale and ii) at larger scales using coarse-graining.

The chemical environment can critically affect the fracture processes, leading to subcritical crack growth. The inner surfaces of the cracks are covered by adsorbates from the surrounding liquid or gas phase. When bonds break in the course of crack propagation, these adsorbates strongly react with the newly created surfaces, for example, by saturating the broken bonds. Examples are stress corrosion cracking in metals and semiconductors or the moisture-driven crack growth in silica. In both cases, the crack propagation induces and drives the incorporation of oxygen species, leading to an oxidation/hydroxylation of the inner surfaces, which completely alters the chemistry at the crack tip.

In this project we propose to study the complex interplay between bond breaking at the crack tip and the adsorption/bond saturation with molecules from the environment by MD simulations. The aim is to obtain mechanistic insights into environmentally-assisted fracture for model ceramic materials.

The mechanical properties and the fracture toughness of polymers can be increased by adding silica nanoparticles. This increase is mainly caused by the development of localized shear bands, initiated by the stress concentrations due to the silica particles. Other mechanisms responsible for the observed toughening are debonding of the particles and void growth in the matrix material. The particular mechanisms depend strongly on the structure and chemistry of the polymers and will be analysed for two classes of polymer-silica composites, with highly crosslinked thermosets or with biodegradable nestled fibres (cellulose, aramid) as matrix materials.

The aim of the project is to study the influence of different mesoscopic parameters, as particle volume fraction, on the macroscopic fracture properties of nanoparticle reinforced polymers.

Interface failure in both tension and shear is characterized by a dynamic interplay of local processes (breaking of bonds, interface contacts or – in case of frictional interfaces – asperities) and long-range elastic load re-distribution which may occur either quasi-statically or in a dynamic manner associated with wave propagation phenomena and can be mapped onto a network of partly break-able load transferring elements. This interplay may give rise to complex dynamics which are strongly influenced by contact geometry and also the chemical properties of the interface. A particularly simple case is the transition from static to sliding friction between continuous bodies where such dynamic collective phenomena are being discussed under the label of ‘detachment waves’.

The goal of P7 is to generalize this concept of ‘detachment waves’ to general problems of failure of frictional or adhesive joints, and to interfaces and bodies which possess a complex multi-scale chemical or geometrical structure, including hierarchical geometrical structures as encountered in biosystems.

https://www.idc.tf.fau.de/neues-graduiertenkolleg-symocads/

Composite systems can allow for combinations of properties that cannot or hardly be found for homogenous compounds. For this purpose, the project is supposed to combine coordination polymers or MOFs with nano to microscale particle systems for the synthesis of composite systems. Therefore, it will be expanded to a joint project of two applicants of the respective expertise. The aimed-at composites shall exhibit simultaneous optical and magnetic properties, e.g. by combination of luminescence with superparamagnetism. In order to achieve this, different external stimuli will be investigated to contact the components, which –in addition to mechanochemistry of the first funding period- will also contain other mechano-related influences, such as spray drying or sonochemistry. Common preliminary work shows that highly interesting to surprising properties can result from the combination of luminescent MOFs and magnetic particles. Especially mechanochemistry seems to have an enormous potential for the combination of both material classes. The influence of different components, synthesis parameters as well as the resulting structure and architecture of the new hybrids will be investigated, and the physical properties determined. In addition, the project will attempt to develop controlled influencing of the core-shell architecture and thereby the sequence of core/shell vs. shell/core depending on variation of MOFs, particle systems, nanoparticle types and supraparticle architectures as well as the synthesis conditions. Altogether, the results of the first funding period will thereby be consequently utilized and further developed in order to get an overview on the formation of such composites, as the latter are both highly interesting for fundamental research as well as for applications, e.g. for in sensing.

The storage of (renewable) electricity in chemical form (fuels) and its subsequent release occur in electrochemical devices such as electrolyzers and fuel cells. An economically viable exploitation of these devices requires electrode materials and architectures that are not only performant but also durable. However, electrocatalyst materials used to date are prone to corrosion and the factors affecting their stability in real electrode, which are complex multiphase entities, are not well understood. The project addresses this aspect by proposing a well-defined model system for these complex materials, one in which the effects of various factors on electrode stability can be investigated systematically. Our preparation combines an ‘anodic’ macroporous template which defines a three-dimensional geometry, polyaniline (PANI) as conductive matrix, and laser-deposited metal nanoparticles embedded in hydrogenated carbon phase (M@C) as the catalyst. We will quantify the performance and stability of these electrodes upon continuous electrolysis and compare similar electrodes differing in (1) nature of interaction between templates and polyaniline matrix; (2) nature of interaction between PANI and hydrogenated carbon phase; (3) architecture of electrode (planar films or tubes obtained on 3D template); (4) geometry of electrode (length and diameter of the tubes). The results of the comparisons will allow us to identify the most promising strategies for improving the stability of real electrodes without sacrificing performance. This ambitious goal is rendered possible by the combination of expertise from the Russian and German teams in the laser-induced deposition of metal/carbon composites and in electrochemical work (including anodization), respectively.

We aimto develop model systems with periodic, interpenetrating networks of electrondonor- and acceptor-phases based on the structural paradigm of metal-organicframeworks (MOFs). The MOFs allow maximum control over the nature of themolecular building blocks with specific electronic properties, their sequenceof assembly, their relative spatial orientation, their wall-thickness, andtheir overall orientation relative to a substrate. The goal of this project isto create such highly defined model systems, to enhance our understanding ofthe relationship between the electronic and structural parameters and theresulting light-induced charge-carrier dynamics, and ultimately to contributeto the understanding and further improvement of solar cells.

The project aims at gathering the fundamental knowledge required for improving the calculation of the service life of solid lubricated rolling bearings, which are typically used in vacuum pumps and rotating
anodes of medical X-Ray devices. The project will specifically focus on MoS₂ tribological coatings. The only service life calculation model available up to date relies on an empirical approach, based on the assessment of the wear rate from macroscopic contact parameters such as load and sliding distance. This model does not capture important processes, such as the progressive transfer and redeposition of coating material onto the uncoated counterpart. The proposed investigations will enable the development of a mechanistic model taking into account the influence of the microstructure, texture and stoichiometry of the coating and relying only marginally on empirical parameters. The primary challenge consists into identifying the fundamental mechanisms governing the deformation of the coating during rolling contact and understanding the consequences in term of material removal, as well as its transfer and deposition onto the uncoated counter-part. This goal will be met by implementing a multi-scale approach closely combining experimental
characterizations with computer simulations. The investigations will focus on two different MoS₂ PVD coatings: the first one featuring a strongly basal texture associated with a coarse microstructure and the
second one a weak texture associated with a fine columnar microstructure. The tribological behavior of these coatings will be investigated at the macroscopic scale by twin-disc tests performed under realistic service conditions. Interrupted monitoring by electron microscopy and atom probe tomography will allow assessing the structural and crystallographic evolution of the coating at the micro and nanoscale as a function of the loading duration. Micromechanical testing will furthermore provide direct insights into the associated deformation and material removal processes. The underlying fundamental mechanisms will finally be revealed by atomistic simulations. As these account for the observed transformation of the coating, they are ultimately responsible for its lifetime, which impliesthat their knowledge will enable formulating a mechanistic model for the service life prediction of MoS2 solid lubricated rolling bearings. The success odds of this project are very high, as the combined expertise of the project partners reaches from tribological
characterization to material characterization, micromechanics, as well as atomistic simulations of surface chemical processes and deformation.

Die Verwendung von Phosphaten in der Herstellung von Wurst ist derzeit nahezu unumgänglich. Phosphate verbessern nicht nur die Konsistenz des Wurstbräts, sondern tragen auch dazu bei, dass ein unerwünschter Austritt von Wasser und Fett aus dem fertigen Produkt verhindert wird. In jüngster Zeit kann die Verwendung dieser Kutterhilfsstoffe jedoch auf eine ablehnende Verbraucherhaltung stoßen, da die Verwendung von Phosphaten deklarationspflichtig ist und somit zu einem negativen Eindruck führen kann. Dem gegenüber stehen Produkte, die mit der sog. "Clean-Label-Kennzeichnung" vereinbar sind. Diese werden von Verbrauchern zunehmend bevorzugt, sodass auch deren Nachfrage stetig steigt.

In einem bereits 2017 bearbeiteten Projekt wurden 20 potentielle Kandidaten analysiert, die als Phosphatalternativen eingesetzt werden könnten. Die erfolgversprechenden Additive wie Leinmehl oder gefriergetrocknete Pilze führten vermutlich auf Grund ihrer eigenen (Re-)Hydratisierung im Testverfahren zu einer Gewichtszunahme und damit Quellung des Bräts. 

Im weiterführenden Projekt sollen nun die Beeinflussung des pH-Wertes von Fleisch sowie die Modulation der verfügbaren Calciumionen im Fleisch Ausgangspunkte zur Verbesserung der Wasserbindekapazität sein. Hierzu soll auf dem Testsystem aus dem bereits abgeschlossenen Projekt aufgebaut werden, welches zukünftig um einen Erhitzungsprozess erweitert werden soll, um auch die Wasserhaltekapazität des erhitzten Produktes beurteilen zu können. Zudem sollen synergistische Effekte, die durch Kombination der erfolgversprechendsten innovativen Additive hervorgerufen werden, untersucht werden.

Ziel des hier vorgestellten Projektes ist es neue und innovative Additive für die Wurstherstellung zu identifizieren, die durch die Beeinflussung des pH-Wertes und/oder der Calciumionenkonzentration die Quellfähigkeit und Wasserhaltekapazität von Wurstbrät verbessern.

The CLATHROPROBES project is devoted to the design and development of novel, highly efficient chiroptical, luminescent, IR, NMR and EPR probes for sensing and structural studies of biomolecules based on cage metal complexes (clathrochelates and lacunar complexes of spatial tris-diiminate ligands with encapsulated 3d-metal ion) as molecular reporters.
For successful design and synthesis of cage metal complexes (WP1), their complete structural and spectroscopic characterization (WP2), studies of their interactions with biomolecules and reporting properties, and their cytotoxicity and bioactivity in model systems (WP3), the project brings together researchers from four academic institutions and two industrial companies, representing six countries (PL, DE, UA, RO and AU; RU - participation till April 8th, 2022). The participants will contribute to the project with different, highly specific, yet complementary expertise, namely in chemical synthesis of clathrochelate complexes (PBMR and FAU; INEOS RAS participation till April 8th, 2022), identification and structural studies of compounds and materials (PBMR, FAU, UWR, UNIVIE, and SPS; INEOS RAS - participation till April 8th, 2022), characterization of interactions between ligands/clathrochelates/materials and biomolecules by CD, UV-VIS, fluorescence ITC, IR, NMR methodology (UWR, FAU, PBMR, UNIVIE, SPS), and biological studies (FAU).
Joint efforts of participants of this multidisciplinary project will provide - the transfer of knowledge between scientists of different research areas, sectors and countries that will enhance level of their professional scientific/technical expertise, -training of young researchers, very important for their further scientific success or industrial career, - enhancement of research activity and network of participating Institutions, - new long-term collaborations between the partners, - increase of academia-industry interactions, so valuable for innovative ideas and discoveries, and pair scientific excellence with social awareness and understanding of current tasks and problems of science.

The overarching goal of the Hy-solFullGraph project is to undertake, from a molecular level, the synthesis of new functional hybrid materials based on carbon allotropes with outstanding properties. Synthetic carbon allotropes (SCAs) are regarded to be among the most promising candidates for future high performance materials. Precise control of the derivatisation will play a key role in tailoring their solubility and reactivity to maximise the advantages of their outstanding …

H2S is a highly toxic and corrosive environmental pollutant, which removal is necessary for pollution control and processing requirements in industry. In our recently filed patent (WO2012175630 A1 20121227) we describe an invention demonstrating that specially modified water soluble Fe, Mn, Co and Ni porphyrins (in particularly, highly positively charged ones) can be used for very efficient catalytic oxidation of H2S by O2 in pH neutral media. There is no need for separate catalyst re-oxidation, because catalysts are automatically regenerated by O2 present in the surrounding medium at ambient conditions. The catalytic reaction transforms H2S into either solid (elemental sulfur) or soluble products (sulfite/thiosulfate), the choice of which can be tuned by choosing appropriate pH conditions. But, elementary reaction steps behind the catalytic activity of certain metalloporphyrins, as well as the character of the intermediate species and the rate-determining steps are completely unknown. Elucidation of these points will provide the understanding of the factors that are responsible for the catalytic vs. stoichiometric reactivity of different types of metalloporphyrins. As scientists we are not just satisfied with a potential application of our findings and therefore we seek for mechanistic explanations on molecular level to rationally design catalytically active metal complexes based on understanding of their kinetic, thermodynamic, solution and redox behavior. Thus, the proposed studies involve careful examination and kinetic/thermodynamic analysis of each reaction step occurring in the course of the oxidation of the H2S/HS¿ mixtures at different pH by O2, with the application of selected series of water-soluble metalloporphyrins as catalysts. Moreover, the intended investigations will be associated with the identification and characterization of the chemical nature of the reactive intermediates responsible for the oxidation events, as well as with the examination of the catalytic ability of the active species as a function of various factors originating both from the chemical identity of the applied porphyrin catalyst (effects of the porphyrin ring, metal center, its spin-state and axial ligands) and from the selected reaction conditions (temperature, pH or polarity of the reaction medium, concentration of dioxygen and catalyst, etc). Special attention will be paid to the redox properties of the investigated highly charged metalloporphyrins as a function of pH and axial ligands, in order to address the question of inner- vs. outer-sphere electron transfer mechanism. Such systematic mechanistic studies of the catalytic H2S oxidation by metalloporphyrins at the molecular level have not yet been addressed in the literature. Besides the relevance in terms of environmentally and economically acceptable technologies, proposed research will also lead to advances in our understanding of biological effects of H2S.

Ionische Flüssigkeiten (engl. Ionic liquids, ILs) sind geschmolzene Salze mit Schmelzpunkten unterhalb von 100°C. Ihre strukturelle Vielfalt eröffnet nahezu unbegrenzte Möglichkeiten für die Kombination von Kationen und Anionen mit unterschiedlichen Eigenschaften. Dies erlaubt die gezielte Variation der physikalisch-chemischen Eigenschaften über einen weiten Bereich und die Anpassung an spezifische Anforderungen. Nachdem anfänglich nur die Volumeneigenschaften der ILs im Vordergrund standen, wurde mittlerweile auch die Bedeutung der Grenzfläche mit ihrer Umgebung für eine Vielzahl von Anwendungen erkannt, insbesondere auch für neue Konzepte in der Katalyse. Wegen ihres niedrigen Dampfdruckes können ILs mit Ultrahochvakuum-basierten Methoden untersucht werden; als Folge beginnt sich der Bereich der Ionic Liquid Surface Science als eigene Subdisziplin zu etablieren. Die Gruppe des Antragstellers hat hierzu signifikant beigetragen, insbesondere auf dem Gebiet der winkelaufgelösten Photoelektronenspektroskopie. Die bisherigen Untersuchungen betreffen im Wesentlichen spezifische Eigenschaften für ausgewählte Systeme, ein allgemeines Verständnis der zugrundeliegenden Mechanismen und Triebkräfte fehlt aber meist. Dieser Mangel an grundlegendem Wissen über die Eigenschaften von IL/Gas (bzw. IL/Vakuum) Grenzflächen, IL/Festkörper-Grenzflächen und von Prozessen in IL Multiphasensystemen ist der Ausgangspunkt für das vorliegende Projekt. Vier Themenbereiche sollen untersucht werden: 1) Temperaturabhängigkeit von Oberflächenzusammensetzung, Oberflächenorientierung und Anreicherungseffekten: adressiert die molekulare Orientierung an der IL Oberfläche, die Oberflächenzusammensetzung binärer IL Mischungen, und den Einfluss von Volumenphasenübergängen auf die Oberflächenorientierung. Die Temperaturabhängigkeit dieser Effekte ist von größter Wichtigkeit für viele Anwendungen, wurde bisher aber in Oberflächenuntersuchungen weitgehend ignoriert. 2) Lösung von Metallkomplexen: befasst sich mit der Entwicklung von Konzepten, um die meist geringe Löslichkeit dieser Komplexe in ILs zu verbessern und insbesondere eine hohe Oberflächenaktivität der Metallkomplexe zu erreichen. Wir werden komplexe Liganden mit IL-artigen Gruppen einsetzen und Metall-enthaltende Komplexe untersuchen. 3) IL/Support Wechselwirkungen: betreffen die Grenzfläche von ILs mit Festkörperoberflächen oder der Oberfläche einer zweiten IL; für diese Untersuchungen werden neben bestehenden in situ Verfahren auch neue Techniken zur Herstellung ultradünner IL Filme eingesetzt werden. 4) Verfolgung chemischer Reaktionen in IL-basierten Systemen: macht sich das Potential der Röntgenphotoelektronenspektroskopie für in situ Untersuchungen zu Nutze. Wir werden Reaktionen zwischen ILs, die Metallierung von Freie-Base-Porphyrinen und die Adsorption und Reaktion kleiner Moleküle an, in der IL gelösten, Metallkomplexen untersuchen.

Cobalt oxide has recently turned out to be a novel, highly active heterogeneous catalyst for key processes in future energy and environmental technology. This includes e.g. low-temperature CO oxidation, the related PROX reaction (preferential oxidation of CO in excess H2), the total oxidation of VOCs (volatile organic compounds), and the reforming of hydrocarbon oxygenates for hydrogen production. Most importantly, cobaltoxide- based catalysts hold a unique potential for replacing or reducing the demand for critical materials (noble metals and rare earth oxides). Despite these outstanding prospects, the origin of the surprising cobalt oxide surface chemistry has remained a mystery up to date. Neither the extreme dependence of activity on surface structure nor the mechanisms by which metal (e.g. Pd) and oxide (e.g. CeO2) modifiers enhance stability and activity are truly understood. The aim of this joint project is to acquire an understanding of the catalytic activity of cobalt oxide materials at the molecular level. Towards this aim the project partners bring together the complementary expertise for a state-of-the-art model catalysis (surface science) approach: (A) the atomic-level structural characterization of reactive sites on complex model catalysts, (B) mechanistic and microkinetic studies of catalytic reactions under UHV conditions, and (C) transfer of this knowledge to realistic reaction conditions by in-situ spectroscopy up to realistic ambient pressure conditions. We will take advantage of the leading expertise of one project partner in preparation of ordered cobalt oxide films, providing access to a unique library of bulk and surfaces structures. We will probe adsorption and reaction on these surface structures, characterize relevant defects at the atomic scale with respect to their geometric and electronic properties, and subsequently modify these structures by metal (Pd) and oxide (CeO2) cocatalysts. In this project, we will mainly focus on low-temperature CO-oxidation and PROX, but perform first explorative work towards oxidation and reforming reactions. Simultaneously, we will cross the materials gap and the pressure gap for cobalt oxide catalysts for the first time and, finally, link the obtained knowledge to industrial-grade powder catalysts by in-situ spectroscopy from UHV to realistic reaction conditions. The interdisciplinary approach of this project will allow us to identify structure-functionality relationships of catalytic processes at an unprecedented level of detail and will guide rational strategies towards future development of complex multifunctional cobalt oxide catalysts.

We propose the development of modern wet chemical concepts for the mass production and chemical modification of graphene - a rapidly rising star on the horizon of materials science - opening the door for superior but still elusive applications such as transparent electrodes, field effect transistors, solar cells, gas sensors and polymer enforcement. Owing to its spectacular electronic properties graphene is expected to be the most promising candidate to replace classical Si-technology and no longer requires any further proof of its importance in terms of fundamental physics. However, fully exploiting the proposed applications requires the availability of processable graphene in large quantities, which generally has been considered to be an insurmountable challenge. This is where the GRAPHENOCHEM project sets in. Our laboratory has been pioneering and is at the forefront of carbon allotrope chemistry. After having investigated basic principles for the functionalization of the 0-dimensional fullerenes and the 1-dimensional carbon nanotubes, which lead to synthesis of numerous examples of derivatives with tailor made properties, we recently started successfully with the investigation of wet chemical approaches for the efficient production of graphene sheets using graphite as an inexpensive starting material. The strategy of GRAPHENOCHEM is to combine chemistry, nanotechnology and materials science to establish highly efficient protocols for the mass production of soluble graphene and the subsequent processing to a whole variety of thins films, composites and devices with outstanding properties. To our knowledge we are the first synthetic organic chemists facing this challenge. We propose to go through the following sequential key objectives, namely: Development of efficient protocols for the mass production of soluble single layer graphene, cloning of graphene, chemical functionalization and doping of graphene, and engineering of graphene based materials and devices.

Graphene confined in one dimensional spaces, e.g. ribbons, represents one of the most promising materials for nanoscale semiconductor devices. However, convenient methods of producing such materials on surfaces suitable for device manufacture are lacking. A new oligomer approach to the synthesis of graphene ribbons on semiconductor surfaces is proposed, based upon oxidative aryl-aryl coupling reactions and Diels-Alder chemistry. This method will surpass current approaches based upon high-temperature desilination of silicon carbide or upon high-temperature deposition of carbon atoms for graphene synthesis. Structures will be created through a novel “nanoembossing” technique, which uses hot-tip nanolithography to convert the graphene precursors into functional nanostructures. This technique will take advantage of the tremendous success and extensive literature in synthesizing free-standing graphitic molecules by a number of groups, including those represented here, as well as the new technique of hot-tip nanolithography. The intellectual merit of the proposed activity involves the development of an unprecedented “bottom-up” approach to the synthesis of graphene, using the unique capabilities of a group of four investigators, each of whom supplies a critical piece of technology. The broader impact of the research stems from the potential breakthrough technology proposed, which may open up a new and potentially revolutionary approach to nanocircuit design, and to the strengthening of ties among several heretofore unlinked groups, providing a unique educational experience for Ph.D. students.

Amphiphile Lipofullerene (A.L.F.) sind Fullerenhexaaddukte, die mit Alkylketten und mit hydrophilen Dendronen modifiziert sind. Die Dendrone besitzen als Endgruppen Säurefunktionen. Diese Verbindungen besitzen gegenüber herkömmlichen Amphiphilen einige neue Merkmale, die zu deutlich veränderten Eigenschaften der Liposomen führen. Sie bilden sehr stabile Liposomen, die darüber hinaus im Gegensatz zu herkömmlichen leicht in ihren Aggregationseigenschaften durch Veränderung des pH-Wertes manipuliert werden können. A.L.F. wurden bereits als Co-Lipide in Phospholipidliposomen und auch als Membranbaustein in reinen A.L.F.-liposomen verwendet. Ziel ist es diese neuartigen Liposomen zum Transport hydrophober Wirkstoffmoleküle einzusetzen. Der Transport kann entweder durch Einlagerung der Wirkstoffmoleküle im Inneren der Liposomen oder mit Unterstützung von Ankermolekülen auch an der Außenseite der Liposomen stattfinden. Um erfolgreich zu diesem Ziel zu gelangen ist es von entscheidender Bedeutung die Aggregationseigenschaften der schon von uns synthetisierten A.L.F. und den noch zu synthetisierenden A.L.F. mit Anker detailliert zu untersuchen. Dabei soll neben spektroskopischen Methoden wie NMR- oder UV-VIS-Spektroskopie vor allem die Cryo-Transmissions-Elektronenmikroskopie (Cryo-TEM) und statische bzw. dynamische Lichtstreuung (SLS, DLS) zum Einsatz kommen. Mit Hilfe dieser Methoden wird es möglich sein, die Stabilität und Art der Liposomen in Abhängigkeit von Temperatur, Konzentration und pH-Wert zu untersuchen. Mit den genannten Methoden und analytischer und präparativer Chromatographie (reversed Phase HPLC) soll auch die Einlagerung von hydrophoben Molekülen qualitativ und quantitativ nachgewiesen werden.

Das vorliegende Projekt befaßt sich mit in situ-Röntgenphotoelektronenspektroskopie zur Untersuchung von Adsorptions- und Reaktionsvorgängen an Oberflächen. Die Experimente sollen z.T. unter Verwendung von hochintensiver Synchrotronstrahlung bei BESSY II in Berlin und z.T. im Labor in Erlangen durchgeführt werden. Dazu steht ein neues Elektronenspektrometer mit integriertem überschalldüsenstrahl zur Verfügung. Ein wesentliches Ziel der geplanten Arbeiten ist es, anhand der Untersuchungen zweier Modellreaktionen die Möglichkeiten und Grenzen der höchstaufgelösten in situ-Röntgenphotoelektronenspektroskopie auszuloten, insbesondere in Kombination mit einem überschalldüsenstrahl, der es erlaubt, die Translations- und Vibrationsenergie und den Druck der auftreffenden Gasteilchen über einen großen Bereich zu variieren. Bei den beiden Modellreaktionen handelt es sich um A) die Dissoziation von Kohlendioxid und Oxidation von Kohlenmonoxid zu Kohlendioxid und B) die Dehydrogenierung und Hydrogenierung einfacher Kohlenwasserstoffe, jeweils auf verschiedenen Metalloberflächen. Die Messungen können statisch (d.h. im Adsorptions-Desorptionsgleichgewicht) bei Anliegen eines bestimmten Druckes vor der Probe oder dynamisch (d.h. während der Adsorption oder Reaktion bei einer festen Temperatur oder beim Durchlaufen einer Heizrampe) untersucht werden. Typische Meßzeiten für ein Spektrum bei dynamischen Messungen liegen bei ca. 5 Sekunden.

Our senses are gateways to the past. Although museums are slowly discovering the power of multi-sensory presentations, we lack the scientific standards, tools and data to identify, consolidate, and promote the wide-ranging role of scents and smelling in our cultural heritage. In recent years, European cultural heritage institutions have invested heavily in large-scale digitization. A wealth of object, text and image data that can be analysed using computer science techniques now exists. However, the potential olfactory descriptions, experiences, and memories that they contain remain unexplored. We recognize this as both a challenge and an opportunity. Odeuropa will apply state-of-the-art AI techniques to text and image datasets that span four centuries of European history. It will identify the vocabularies, spaces, events, practices, and emotions associated with smells and smelling. The project will curate this multi-modal information, following semantic web standards, and store the enriched data in a ‘European Olfactory Knowledge Graph’ (EOKG). We will use this data to identify ‘storylines’, informed by cultural history and heritage research, and share these with different audiences in different formats: through demonstrators, an online catalogue, toolkits and training documentation describing best-practices in olfactory museology. New, evidence-based methodologies will quantify the impact of multisensory visitor engagement. This data will support the implementation of policy recommendations for recognising, promoting, presenting and digitally preserving olfactory heritage. These activities will realize Odeuropa’s main goal: to show that smells and smelling are important and viable means for consolidating and promoting Europe’s tangible and intangible cultural heritage.

This Flagship aims to take graphene and related layered materials from a state of raw potential to a point where they can revolutionize multiple industries - from flexible, wearable and transparent electronics, to new energy applications and novel functional composites.Our main scientific and technological objectives in the different tiers of the value chain are to develop material technologies for ICT and beyond, identify new device concepts enabled by graphene and other layered materials, and integrate them to systems that provide new functionalities and open new application areas.These objectives are supported by operative targets to bring together a large core consortium of European academic and industrial partners and to create a highly effective technology transfer highway, allowing industry to rapidly absorb and exploit new discoveries.The Flagship will be aligned with European and national priorities to guarantee its successful long term operation and maximal impact on the national industrial and research communities.Together, the scientific and technological objectives and operative targets will allow us to reach our societal goals: the Flagship will contribute to sustainable development by introducing new energy efficient and environmentally friendly products based on carbon and other abundant, safe and recyclable natural resources, and boost economic growth in Europe by creating new jobs and investment opportunities.

This joint experimental and theoretical project aims at the development of facile and environmentally friendly organocatalytic multi-step domino reactions exploiting dispersion interactions in these novel systems. We plan to conduct a series of multi-component domino reactions involving readily available nitroolefins and aldehydes, as well as CH-acidic malononitrile already known for its broad application and its versatile use as an exceptionally reactive compound. We will mainly focus on the following three unprecedented reactions: (i) three-component two-step domino Knoevenagel/vinylogous Michael reaction; (ii) three-component five-step branched domino Knoevenagel/nitro-Michael/nitroalkane-Michael/intramolecular condensation/isomerization; (iii) two-component six-step domino Knoevenagel/dimerisation/ intermolecular condensation/intramolecular aza-Michael/intramolecular condensation/ isomerization reaction. Detailed mechanistic investigations will be performed using conventional density-functional methods in conjunction with semiempirical van der Waals corrections as well as novel highly accurate density-functional methods to shed light on the intriguing differences in chemoselectivity, regioselectivity and stereoselectivity in these organocatalysed domino transformations, and, in particular, to understand and exploit the influence of dispersion interaction in these transformations. Taking the envisioned domino reactions as test cases, computational setups for a density-functional based description of organocatalysis will be developed.

Planar transition metal complexes, such as porphyrins and phthalocyanines, adsorbed on solid supports are interesting systems for sensors and heterogeneous catalysis. An important feature of these complexes, compared to supported metal clusters, is the fact that the active sites, i.e., the coordinated metal centers with their vacant axial coordination sites, are well-defined and uniform. From the application point of view, this promises high selectivity, and from the research point of view easier interpretation of the data. The topic of funCOS 2 is the electronic structure and chemical properties of tetraphenylporphyrins adsorbed on MgO(100) thin films, characterized with x-ray- UV- and two-photon-photoelectron spectroscopy(XPS, UPS, 2PPE). We will focus on the preparation and characterization of well-ordered porphyrin layers, the reactivity of the metal center of the porphyrins and the changes induced by the adsorption of small molecules on the metal center. We aim to: 1) Prepare well-ordered and fully-oxidized MgO(100) thin films on Ag(100), to control, identify and quantify the type and density of defects and to map out the valence and conduction band with UPS and 2PPE. 2) Investigate the interaction of tetraphenylporphyrin, platinum and cobalt tetraphenylporphyrin and a carboxyl (-COOH) functionalized tetraphenylporphyrin with the MgO(100) surface. Focus will be on changes in the N 1s, Pt 4f, Co 2p and valence and conduction band regions as the coverage is increased from submonolayers to multilayers. 3) Investigate simple reactions with porphyrins on MgO(100) and extract kinetic parameters. Focus will be on metalation and adsorption of small molecules (CO, NO, O2 and H2S) on the metal center and the influence this has on the valence band. 4) Characterize with XPS and UPS two selected high surface area porphyrin/MgO systems from funCOS 5 and investigate to which extent they can be described through the results obtained from the model MgO(100) systems.

 

Knowledge-based design of organic/oxide interfaces requires detailed insights into molecule-oxide bond formation. This project aims at providing this information, combining two complementary surface spectroscopies, surface vibrational spectroscopy (IRAS, infrared reflection absorption spectroscopy) and photoelectron spectroscopy (XPS, X-ray photoelectron spectroscopy), both under UHV (ultrahigh vacuum) conditions.Starting from ordered, atomically clean oxides (MgO(100)/Ag(100), later Co3O4,CoO/Ir(100) and TiO2(110)) we will identify the interaction/reaction mechanisms of selected anchor groups (-OH, -COOH, -NH2, -CN) with specific surface sites using small test molecules. The energetics and kinetics of molecule-oxide bond formation will be studied by temperature-programmed and time-resolved experiments. In a second step, these linkers will be introduced into complex builders (5,10,15,20-Tetraphenypporphyrins, TPP; later other tetrapyrroles) to control their surface interaction. The combined spectroscopic information will provide insight into reaction mechanisms and kinetics during transformation of functional groups and into the energetics and the thermal stability of surface-linked intermediates. Also, we will follow spectroscopically the molecular orientation during film growth, the intermolecular interactions, and related ordering phenomena. Exploration of the linker concept will include multiple coordination through chelating and/or multifunctional units, with the aim of tuning orientation, formation barrier, and thermal stability. In the second project phase we will address the selectivity of molecule-oxide bond formation. Surface linking reactions will be studied with respect to their potential to address specific surface sites by appropriate anchors or anchor ensembles. On nanostructured oxide surfaces (defect structures, supported oxide or metal nanoparticles on oxides) we will aim at preparing nanostructured functional films maintaining a maximum level of control over the growth behavior. Finally, the project will address the reactivity of functional molecular films on oxides and, closely related to this subject, the transferability of knowledge to ambient conditions and nanomaterials. The influence of reactive environments (e.g. H2O, H2, CO, CO2) on surface anchoring (test molecules and substituted TPPs) will be probed in UHV by TPD (temperature programmed desorption spectroscopy) and MB methods (molecular beams), and compared to studies at near-ambient conditions by in-situ spectroscopies (PM-IRAS, polarization modulation IRAS, and, where required, HP-XPS, high pressure XPS). Reactivity studies of complex builders (e.g. with CO, NO, H2O, H2) in UHV and at higher pressure will be performed using the same methods. Finally, we will apply in-situ/operando DRIFTS (diffuse reflection infrared FT spectroscopy) to correlate bond formation and film growth on single-crystal models and on real oxide nanostructures (e.g. MgO nanocrystals).

 

Scanning probe microscopy allows quantitative measurements of structural, mechanical and electronic properties of molecular systems on metal surfaces. Using scanning tunneling microscopy, atoms and molecules can be manipulated in a controlled manner and their electronic density of states is measured.  The forces needed to manipulate and deform individual molecules are often unknown. In this project area, the forces between individual molecules, as well as molecular switches on surfaces, are investigated on a quantitative basis by means of atomic force microscopy and spectroscopy.

Metal-organic charge-transfer complexes based on TCNQ shows exciting electrical or photochemical switching properties, which involves modification of the valence state of TCNQ (TCNQ-/TCNQ°). We use complementary microspectroscopic tools to investigate in-situ the switching behaviour of individual Ag-TCNQ nanocrystals. Structural probes like Nano-XRD and electron diffraction are considered to offer insight into potential structural modifications upon electrical switching.

This Flagship aims to take graphene and related layered materials from a state of raw potential to a point where they can revolutionize multiple industries - from flexible, wearable and transparent electronics, to new energy applications and novel functional composites.Our main scientific and technological objectives in the different tiers of the value chain are to develop material technologies for ICT and beyond, identify new device concepts enabled by graphene and other layered materials, and integrate them to systems that provide new functionalities and open new application areas.These objectives are supported by operative targets to bring together a large core consortium of European academic and industrial partners and to create a highly effective technology transfer highway, allowing industry to rapidly absorb and exploit new discoveries.The Flagship will be aligned with European and national priorities to guarantee its successful long term operation and maximal impact on the national industrial and research communities.Together, the scientific and technological objectives and operative targets will allow us to reach our societal goals: the Flagship will contribute to sustainable development by introducing new energy efficient and environmentally friendly products based on carbon and other abundant, safe and recyclable natural resources, and boost economic growth in Europe by creating new jobs and investment opportunities.

Das Ziel von funCOS 4 ist ein vertieftes Verständnis der fundamentalen Prozesse beim Wachstum von unterschiedlich synthetisierten organischen Dünnschichtsystemen auf Oxidoberflächen (einkristalline Substrate, nanostrukturierte Substrate, amorphe Substrate). Dies beinhaltet Wechselwirkungsphänomene, insbesondere das Zusammenspiel zwischen intermolekularen Wechselwirkungen und Molekül-Substrat-Wechselwirkung, die maßgebend für das Wachstum von organischen ultradünnen Filmen sind. Die strukturellen Eigenschaften dieser adsorbierten organischen Filme von Submonolagenbedeckung bis Multilagen werden durch Methoden erforscht, die Informationen von atomaren bis mesoskopischen Längenskalen erlauben. Beugungsmethoden (XRD/LEED) bestimmen die strukturellen Parameter mit Genauigkeiten besser als 0,01 nm, und in in situ-Studien kann die Kinetik des Filmwachstums verfolgt werden. Anhand diverser mikroskopischer Methoden (PEEM, STXM, LEEM) kann sowohl der Wachstumsmodus (Lagen vs. Insel vs. Random) als auch die Kinetik des Filmwachstums im Realraum mit Auflösungen auf mesoskopischen lateralen Längenskalen von 20 bis 10.000 nm bestimmt werden. Dieses Projekt wird die Lücke zwischen im Ultrahochvakuum synthetisierten Modellsystemen und aus Lösung abgeschiedenen molekularen Lagen schließen. Damit können potentielle Routen aufgezeigt werden, um kostengünstig hochgeordnete molekulare Systeme zu synthetisieren. Insbesondere werden wir das strukturelle Wachstum von adsorbierten/chemisorbierten ultradünnen Filmen (vertikale und laterale Struktur, molekulare Orientierung), die strukturellen Parameter der Molekül/Oxid-Grenzfläche, die Bedeutung von Defektstrukturen, strukturelle Relaxationen in Abhängigkeit von Dichte und Dicke, die Wachstumsmodi, die Nukleation und langreichweite Wechselwirkungen und die kinetischen Parameter des Filmwachstums untersuchen.

With the help of electronic structure calculations, the project aims at a comprehensive theoretical understanding at the microscopic level of the adsorbate-substrate and adsorbate-adsorbate interactions of functionalized organic molecules on structured oxide surfaces, which eventually shall enable a controlled formation of organic films with specific structural, electronic and optical properties. The first basic interaction, the adsorbate-substrate interaction, is the bonding of organic molecules to pristine oxide surfaces or to low-coordinated sites on structured oxide substrates and the variation of this binding by different linker groups that modify the bonding geometry and strength, which, subsequently, may influence the second important interaction, the adsorbate-adsorbate interaction, as well as the diffusion kinetics and structure formation. The different interactions shall be calculated and analyzed with density-functional methods supplemented by Van-der-Waals corrections and, where necessary, by Hubbard-U approaches. For the investigation of structure formation also semi-empirical methods shall be employed, which enable the treatment of large molecular assemblies on structured oxide surfaces. Adsorbed organic molecules may show new photo-physical and electronic properties originating from the interaction of their frontier states with the substrate electronic structure. Another aim of the project is to analyze and understand these modifications of the molecules and to unravel possible charge transfer processes between the adsorbate and the substrate that are pivotal for applications encompassing photovoltaics, sensing, illumination, and photo-chemistry. To that end, based on density-functional calculations, time-dependent density-functional methods and many-body perturbation-theory methods shall be applied.

 

M3d is a FP7 European project aiming at developing advanced magnetic materials suitable for designing a data storage solution in three dimensions (3D). Conventional planar (2D) devices are expected to reach the limits of scaling within less than a decade, so that long-term massive progress could only be achieved by exploiting the third dimension. We will develop the materials needed for such 3D memories based on magnetic shift-register devices, namely dense arrays of vertical magnetic wires in a matrix (race-track memory, IBM patent). In this concept series of bits are shifted along each wire, requiring only one read/write element per wire. Synthesis will rely largely on bottom-up routes to minimize production costs. In order to minimize risks, several strategies will be explored both for coding bits, data shifting, read&write schemes. We address NMP data storage call targets density (5-50Tbit/in2), and reasonable cost per Tbit (2-20€), going beyond the scalability of all-planar devices while remaining competitive in terms of speed and energy consumption (1-10GHz with zero seek time; 10-100 pJ/bit). In all four targets, 3D magnetic memories promise to outperform Hard Disk Drives, providing more storage capacity with less energy consumption. The project brings together relevant leading academic research groups in Europe. Two SMEs are also partners, one for material development (SmartMembranes, world leader in self-organized anodized products), and the European leader in Magnetic-RAM development, Crocus Technology.

Das Projekt A1 stellt die Materialbasis für drei Verbindungsklassen (synthetic carbon allotropes – SCA) des SFB sicher, nämlich 1) Fullerene, 2) Kohlenstoffnanoröhren und 3) Graphen und jeweils deren Derivate. Das Projekt ist in drei Arbeitspakete (WPs) unterteilt. Im WP1 wird der erste systematische Zugang zu SCA-Hydriden und –Carboxylaten, einschließlich der Entwicklung von Wasserstoff-Speicher-Systemen, der Postfunktionalisierung und dem effizienten Trennen von metallischen und halbleitenden Kohlenstoffnanoröhren ausgearbeitet werden. Nicht-kovalente Funktionalisierung von SCAs mit verschiedenen Familien von Rylenen ist Gegenstand von WP2. In WP3 werden weitere spezifische SCA-Architekturen, wie kovalente Fulleren-Cluster und hierarchisch geordnete inter-SCA-Architekturen synthetisiert werden.

Ziel des Teilprojektes ist die chemische Modifizierung von Graphenschichten auf Metalloberflächen durch Heteroatome (N, B). Die vorgesehenen Strategien umfassen Voradsorption von N-haltigen (NO, C2N2, Pyridin) oder B-haltigen Molekülen (Diethylmethoxyboran), Dosierung reaktiver Spezies mit einem überschalldüsenstrahl, Funktionalisierung mit Rylenen und Porphyrinen, Hydrogenierung zu Graphan und Interkalation von Metallen. Darüber hinaus soll auch die in situ Synthese makromolekularer Strukturen auf Metalloberflächen untersucht werden. Als experimentelle Methode wird hauptsächlich Röntgenphotoelektronenspektroskopie eingesetzt werden.

Im Projekt sollen Kohlenstoffmaterialien, Fullerene, Polyine, Graphene wie auch bisher noch nicht synthetisierte Kohlenstoffallotrope wie beispielsweise Graphyne mit nichtempirischen elektronischen Strukturmethoden insbesondere etablierten wie neu zu entwickelnden Dichtefunktionalmethoden untersucht werden. Mit dem Ziel neue Kohlenstoffverbindungen und -materialien herzustellen sollen deren Bildung, Struktur und Energetik wie auch ihre spektroskopischen und elektronischen Eigenschaften analysiert und vorhergesagt werden.

Ziel des Projektes ist die Entwicklung und Anwendung von schnellen parametrisierten quantenmechanischen Techniken (semiempirische Molekülorbital-Theorie und Dichtefunktional-basiertes tight binding, TB), um große Aggregate, die Kohlenstoff-Allotrope enthalten, zu berechnen und Reaktionsmechanismen zu bestimmen. Die dynamischen Eigenschaften von flexiblen molekularen Anordnungen werden sowohl mit klassisch-mechanischer als auch mit direkter TB Moleküldynamik und Metadynamik untersucht. Es werden sowohl Systeme aus den experimentellen Projekten untersucht als auch Strukturen, Wellenfunktionen und Elektronendichten für die anderen theoretischen Teilprojekte berechnet.

Synthetic carbon allotropes such as fullerenes, carbon nanotubes and graphene currently represent one of the most promising materials families with enormous potential for high-performance applications in the fields of nanoelectronics, optoelectonics, hydrogen storage, sensors and reinforcements of polymers based on their unprecedented electronic, optical, mechanical and chemical properties. Because of the almost limitless possibilities of constructing both discrete and extended networks of sp-, sp2- and sp3-hybridised C-atoms, many additional and so far unknown modifications with remarkable properties can be imagined and have been predicted. Tapping these exciting possibilities fully, however, still requires overcoming a number of significant hurdles such as high-yield production methods, sorting and separation, developing synthesis protocols for new carbon allotropes, controlled doping with heteroelements, solubilisation, chemical functionalisation, hierarchically ordered architectures and layer (single and multiple) formation. Hence tremendous interdisciplinary efforts are required that systematically combine the expertise of chemists, physicists, engineers and theoreticians, together with the contributions of high-end analytical instrumentation. The University of Erlangen-Nürnberg hosts probably the largest and most productive pioneering community in Europe or even worldwide at the forefront of carbon allotrope research. As a consequence Erlangen is the ideal place for the Collaborative Research Centre. The programme is structured according to three research areas and two central projects. Research area A "Synthesis and Functionalisation" provides the materials basis of the programme. Chemical functionalisation of existing synthetic carbon allotropes and development of new carbon modifications both lie at the forefront of this effort. The next level within the process chain is the systematic investigation of physical and materials properties and the development of concepts for device fabrication. This is guaranteed by the close interaction with research area B "Electronic, Optical and Structural Properties" and the two scientific central projects on high-resolution electron microscopy and tandem mass spectrometry. This highly integrated and interdisciplinary approach of the Collaborative Research Centre also necessitates a close connection with research area C "Theory". Both classical and quantum mechanical calculations provide the basis for an in-depth understanding of reaction mechanisms, stability as well as electronic, optical, structural and mechanical properties of synthetic carbon allotropes and their derivatives. Moreover, theory will provide some of the most valuable design principles for the exploration of hitherto unknown forms of carbon.