In summation, this thesis provides a panoramic view of the prevailing challenges and potential solutions associated with achieving unparalleled energy and power densities in GDIBs where graphite reigns supreme as the cathode material of choice. By comprehensively tackling these challenges and integrating the recommended strategies, there lies a promising path ahead for the evolution of advanced dual-ion batteries. Such advancements could redefine benchmarks in en-ergy storage, heralding an era of more efficient and versatile applications.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a new generation of conduct-ing MOFs for electronics. However, controlled synthesis of thin-film samples with high crystallinity and defined layer orientation, which is beneficial for achieving high-performance devices and reliable structure-property relationship, has remained a challenge. Here we develop a surfactant-directed two-step synthesis of layered 2D c-MOF films based on benzene and triphenylene ligands linked by copper-bis(diimino) complexes (HIB-Cu and HITP-Cu, respectively). The achieved layered 2D c-MOF films are featured as free-standing, in-plane oriented, and polycrystalline films with domain size up to ~ 8000 nm2 and a tunable thickness in the range of 8 - 340 nm. Benefiting from the intrinsic elec-trical conductivity and quasi-one-dimensional pore channels, a HIB-Cu film based chemiresistive sensor is construct-ed, displaying effective humidity sensing with a response as fast as ~ 21 s, superior to the reported MOF-powder-based chemiresistive sensors (in the orders of minutes).

Correction to: Nature https://doi.org/10.1038/s41586-021-03842-3

This thesis focused on the synthesis and characterization of novel functional materials based on cellulose and graphene derivatives. Cellulose/GO hydrogels were produced as the starting material by dissolving cellulose and dispersing GO in NaOH/urea solution. This method is considered as an efficient, simple, environmentally friendly, and low-cost method. Novel functionalities, such as sensing, catalytic and EMI shielding properties have been “built-in” to cellulose/GO hydrogels. Cellulose/rGO composite films and aerogels were successfully fabricated by dissolving cellulose and dispersing GO in NaOH/urea solution, followed by the chemical reduction with vitamin C as the reducing agent. The cellulose/rGO films and aerogels with various rGO contents were prepared by air-drying and freeze-drying of the prepared cellulose/rGO composite hydrogels. The resultant cellulose/rGO composites prepared by this efficient and simple method show high resistance sensitivity to environmental stimuli like temperature, humidity, liquids, vapours, and strain stress. Thus, the cellulose/rGO films can be applied in detecting human motions and human breath cycles. Liquid temperature, liquid type, and ion concentration also be determined by our cellulose/rGO films. Moreover, the composite aerogels are fast responding and extremely sensitive sensors for vapour detection and testing with good repeatability. It was also revealed that discriminating and quantitative responses can be obtained when analyzing various vapours and different vapour concentrations. For methanol vapour, the aerogel shows linear response to the vapour concentration. Thus cellulose/rGO composite aerogel can be used to quantify methanol vapour concentrations. The efficient, scalable, and environmentally friendly preparation of novel and high-performance of vapour sensing materials with well reproducibility is promising to achieve practical vapour sensing applications. We have successfully presented an effective, facial, simple, and scalable method to form Fe3O4 nanoparticles onto cellulose/GO hydrogels. XRD, FTIR, XPS and TEM indicated that Fe3O4 nanoparticles with good dispersion and uniform size are successfully coated on cellulose matrix and GO sheets. This material was tested as catalyst for the cleaning of dye-contaminated water by oxidation with H2O2.The optimized experiment conditions for AO7 degradation are: [AO7] = 0.1 mM, T = 298 K, [H2O2] = 22 mM, and pH = 3. Under these conditions, the resulting hydrogels display 97 % AO7 removal within 120 min and retained strong degradation performance after twenty consecutive cycles of reuse. Especially, the detailed XPS analysis of cellulose/GO/Fe3O4 and cellulose/Fe3O4 composites indicated that the cellulose/GO/Fe3O4 hydrogel retain its high degradation activity by keeping the ratio of Fe3+/Fe2+ at 2 during the 20 heterogeneous Fenton-like reaction cycles. Therefore, the cellulose/GO/Fe3O4 hydrogel is recommended to test the treatment of other dye-contaminated wastewaters. Cellulose/rGO/Fe3O4 films and aerogels were successfully fabricated by the in-situ grown of Fe3O4 nanoparticles within a cellulose matrix containing rGO sheets. Cellulose/rGO (8 wt.%)/Fe3O4 aerogels with the thickness of 0.5 mm exhibited high EMI shielding performance with the EMI SE value at 32.4-40.1 dB in the 8.2-12.4 GHz frequency range. High loading of rGO and large thickness of the composites are beneficial for the excellent EMI shielding performance of our aerogels. The lightweight aerogel is suitable for the practical application as EMI shielding materials such as spacecraft, aircraft, energy conversion application, and energy storage.

We describe an efficient synthesis of the methylene-bridged biscarbazole alkaloids bismurrayafoline-A, bismurrayafolinol and chrestifoline B–D using an Ullmann-type coupling at the benzylic position.

Advances in flexible and functional metal–organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009–2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host–guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal–organic frameworks for separation, catalysis, sensing, and biomedicine.

Soft lithographic methods describe a set of printing methods which are widely used for the preparation of structured surfaces. Structured surfaces are essential components in the field of (opto-)electronic devices such as organic light emitting diodes, photovoltaics or organic field effect transistors. In recent years, crucial progress has been achieved in the development of patterned metal coatings for these applications. This review focusses on new strategies for soft lithographical printing of metal structures emphasizing the subtle interplay of printing techniques, metal precursor chemistry, and surface functionalization strategies. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

We report on the surface-catalyzed formal [2+2] and [2+2+2] cycloadditions of ortho-activated tetracene species on a Ag(111) substrate under ultrahigh vacuum conditions. Three different products are obtained: tetracene dimers, trimers, and tetramers. The former results from the formation of a four-membered ring while the other two arise from cyclization into six-membered rings. These on-surface reactions have been monitored by scanning tunneling microscopy and rationalized by density functional theory calculations. Our approach, based on the reaction of ortho-dihalo precursor monomers via formal cycloadditions, establishes an additional method for the highly active field of on-surface synthesis and enables the development of novel 1D and 2D covalent carbon nanostructures.

The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closedshell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spinbased operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and onsurface synthesis of π-extended triangulene, a non-Kekulé nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state. The structure of individual molecules adsorbed on an inert gold surface is confirmed through ultrahigh-resolution scanning tunneling microscopy. The electronic properties are studied via scanning tunneling spectroscopy, wherein unambiguous spectroscopic signatures of the spin-split singly occupied molecular orbitals are found. Detailed insight into its properties is obtained through tight-binding, density functional and many-body perturbation theory calculations, with the latter providing evidence that π-extended triangulene retains its open-shell quartet ground state on the surface. Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, potentially useful in carbon-based spintronics.

Nonbenzenoid carbocyclic rings are postulated to serve as important structural elements toward tuning the chemical and electronic properties of extended polycyclic aromatic hydrocarbons (PAHs, or namely nanographenes), necessitating a rational and atomically precise synthetic approach toward their fabrication. Here, using a combined bottom-up in-solution and on-surface synthetic approach, we report the synthesis of nonbenzenoid open-shell nanographenes containing two pairs of embedded pentagonal and heptagonal rings. Extensive characterization of the resultant nanographene in solution shows a low optical gap, and an open-shell singlet ground state with a low singlet–triplet gap. Employing ultra-high-resolution scanning tunneling microscopy and spectroscopy, we conduct atomic-scale structural and electronic studies on a cyclopenta-fused derivative on a Au(111) surface. The resultant five to seven rings embedded nanographene displays an extremely narrow energy gap of 0.27 eV and exhibits a pronounced open-shell biradical character close to 1 (y0 = 0.92). Our experimental results are supported by mean-field and multiconfigurational quantum chemical calculations. Access to large nanographenes with a combination of nonbenzenoid topologies and open-shell character should have wide implications in harnessing new functionalities toward the realization of future organic electronic and spintronic devices.