Electrochemical Investigation of Calcium Substituted Monoclinic Li3 V2 (PO4 )3 Negative Electrode Materials for Sodium- and Potassium-Ion Batteries.

Herein, the electrochemical properties and reaction mechanism of Li3-2 x Cax V2 (PO4 )3 /C (x = 0, 0.5, 1, and 1.5) as negative electrode materials for sodium-ion/potassium-ion batteries (SIBs/PIBs) are investigated. All samples undergo a mixed contribution of diffusion-controlled and pseudocapacitive-type processes in SIBs and PIBs via Trasatti Differentiation Method, while the latter increases with Ca content increase. Among them, Li3 V2 (PO4 )3 /C exhibits the highest reversible capacity in SIBs and PIBs, while Ca1.5 V2 (PO4 )3 /C shows the best rate performance with a capacity retention of 46% at 20 C in SIBs and 47% at 10 C in PIBs. This study demonstrates that the specific capacity of this type of material in SIBs and PIBs does not increase with the Ca-content as previously observed in lithium-ion system, but the stability and performance at a high C-rate can be improved by replacing Li+ with Ca2+ . This indicates that the insertion of different monovalent cations (Na+ /K+ ) can strongly influence the redox reaction and structure evolution of the host materials, due to the larger ion size of Na+ and K+ and their different kinetic properties with respect to Li+ . Furthermore, the working mechanism of both LVP/C and Ca1.5 V2 (PO4 )3 /C in SIBs are elucidated via in operando synchrotron diffraction and in operando X-ray absorption spectroscopy.

Metal-Organic Framework Thin Films as Ideal Matrices for Azide Photolysis in Vacuum.

Studies on reactions in solutions are often hampered by solvent effects. In addition, detailed investigation on kinetics is limited to the small temperature regime where the solvent is liquid. Here, we report the in situ spectroscopic observation of UV-induced photochemical reactions of aryl azides within a crystalline matrix in vacuum. The matrices are formed by attaching the reactive moieties to ditopic linkers, which are then assembled to yield metal-organic frameworks (MOFs) and surface-mounted MOFs (SURMOFs). These porous, crystalline frameworks are then used as model systems to study azide-related chemical processes under ultrahigh vacuum (UHV) conditions, where solvent effects can be safely excluded and in a large temperature regime. Infrared reflection absorption spectroscopy (IRRAS) allowed us to monitor the photoreaction of azide in SURMOFs precisely. The in situ IRRAS data, in conjunction with XRD, MS, and XPS, reveal that illumination with UV light first leads to forming a nitrene intermediate. In the second step, an intramolecular rearrangement occurs, yielding an indoloindole derivative. These findings unveil a novel pathway for precisely studying azide-related chemical transformations. Reference experiments carried out for solvent-loaded SURMOFs reveal a huge diversity of other reaction schemes, thus highlighting the need for model systems studied under UHV conditions.

Guest Ion-Dependent Reaction Mechanisms of New Pseudocapacitive Mg3 V4 (PO4 )6 /Carbon Composite as Negative Electrode for Monovalent-Ion Batteries.

Polyanion-type phosphate materials, such as M3 V2 (PO4 )3 (M = Li/Na/K), are promising as insertion-type negative electrodes for monovalent-ion batteries including Li/Na/K-ion batteries (lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent-ion insertion. Here, triclinic Mg3 V4 (PO4 )6 /carbon composite (MgVP/C) with high thermal stability is synthesized via ball-milling and carbon-thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion-dependent reaction mechanisms of MgVP/C upon monovalent-ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg0 , V0 , and Li3 PO4 in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V3+ to V2+ . Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g-1 (30/19 Li+ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na+ /K+ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent-ion batteries with guest ion-dependent energy storage mechanisms.

Solution Atomic Layer Deposition of Smooth, Continuous, Crystalline Metal-Organic Framework Thin Films.

For the first time, a procedure has been established for the growth of surface-anchored metal-organic framework (SURMOF) copper(II) benzene-1,4-dicarboxylate (Cu-BDC) thin films of thickness control with single molecule accuracy. For this, we exploit the novel method solution atomic layer deposition (sALD). The sALD growth rate has been determined at 4.5 Å per cycle. The compact and dense SURMOF films grown at room temperature by sALD possess a vastly superior film thickness uniformity than those deposited by conventional solution-based techniques, such as dipping and spraying while featuring clear crystallinity from 100 nm thickness. The highly controlled layer-by-layer growth mechanism of sALD proves crucial to prevent unwanted side reactions such as Ostwald ripening or detrimental island growth, ensuring continuous Cu-BDC film coverage. This successful demonstration of sALD-grown compact continuous Cu-BDC SURMOF films is a paradigm change and provides a key advancement enabling a multitude of applications that require continuous and ultrathin coatings while maintaining tight film thickness specifications, which were previously unattainable with conventional solution-based growth methods.

Electrospun carbon nanofibre-assisted patterning of metal oxide nanostructures.

This work establishes carbon nanofibre-mediated patterning of metal oxide nanostructures, through the combination of electrospinning and vapor-phase transport growth. Electrospinning of a suitable precursor with subsequent carbonization results in the patterning of catalyst gold nanoparticles embedded within carbon nanofibres. During vapor-phase transport growth, these nanofibres allow preferential growth of one-dimensional metal oxide nanostructures, which grow radially outward from the nanofibril axis, yielding a hairy caterpillar-like morphology. The synthesis of metal oxide caterpillars is demonstrated using zinc oxide, indium oxide, and tin oxide. Source and substrate temperatures play the most crucial role in determining the morphology of the metal oxide caterpillars, whereas the distribution of the nanofibres also has a significant impact on the overall morphology. Introducing the current methodology with near-field electrospinning further facilitates user-defined custom patterning of metal oxide caterpillar-like structures.

Comparing Carbon Origami from Polyaramid and Cellulose Sheets.

Carbon origami enables the fabrication of lightweight and mechanically stiff 3D complex architectures of carbonaceous materials, which have a high potential to impact a wide range of applications positively. The precursor materials and their inherent microstructure play a crucial role in determining the properties of carbon origami structures. Here, non-porous polyaramid Nomex sheets and macroporous fibril cellulose sheets are explored as the precursor sheets for studying the effect of precursor nature and microstructure on the material and structural properties of the carbon origami structures. The fabrication process involves pre-creasing precursor sheets using a laser engraving process, followed by manual-folding and carbonization. The cellulose precursor experiences a severe structural shrinkage due to its macroporous fibril morphology, compared to the mostly non-porous morphology of Nomex-derived carbon. The morphological differences further yield a higher specific surface area for cellulose-derived carbon. However, Nomex results in more crystalline carbon than cellulose, featuring a turbostratic microstructure like glassy carbon. The combined effect of morphology and glass-like features leads to a high mechanical stiffness of 1.9 ± 0.2 MPa and specific modulus of 2.4 × 104 m2·s-2 for the Nomex-derived carbon Miura-ori structure, which are significantly higher than cellulose-derived carbon Miura-ori (elastic modulus = 504.7 ± 88.2 kPa; specific modulus = 1.2 × 104 m2·s-2) and other carbonaceous origami structures reported in the literature. The results presented here are promising to expand the material library for carbon origami, which will help in the choice of suitable precursor and carbon materials for specific applications.

Reversible Diels-Alder and Michael Addition Reactions Enable the Facile Postsynthetic Modification of Metal-Organic Frameworks.

Functionalization of metal-organic frameworks (MOFs) is critical in exploring their structural and chemical diversity for numerous potential applications. Herein, we report multiple approaches for the tandem postsynthetic modification (PSM) of various MOFs derived from Zr(IV), Al(III), and Zn(II). Our current work is based on our efforts to develop a wide range of MOF platforms with a dynamic functional nature that can be chemically switched via thermally triggered reversible Diels-Alder (DA) and hetero-Diels-Alder (HDA) ligations. Furan-tagged MOFs (furan-UiO-66-Zr) were conjugated with maleimide groups bearing dienophiles to prepare MOFs with a chemically switchable nature. As HDA pairs, phosphoryl dithioester-based moieties and cyclopentadiene (Cp)-grafted MOF (Cp-MIL-53-Al) were utilized to demonstrate the cleavage and rebonding of the linkages as a function of temperature. In addition to these strategies, the Michael addition reaction was also applied for the tandem PSM of IRMOF-3-Zn. Maleimide groups were postsynthetically introduced in the MOF lattice, which were further ligated with cysteine-based biomolecules via the thiol-maleimide Michael addition reaction. On the basis of the versatility of the herein presented chemistry, we expect that these approaches will help in designing a variety of sophisticated functional MOF materials addressing diverse applications.

Polycrystalline texture causes magnetic instability in greigite.

Magnetic stability of iron mineral phases is a key for their use as paleomagnetic information carrier and their applications in nanotechnology, and it critically depends on the size of the particles and their texture. Ferrimagnetic greigite (Fe3S4) in nature and synthesized in the laboratory forms almost exclusively polycrystalline particles. Textural effects of inter-grown, nano-sized crystallites on the macroscopic magnetization remain unresolved because their experimental detection is challenging. Here, we use ferromagnetic resonance (FMR) spectroscopy and static magnetization measurements in concert with micromagnetic simulations to detect and explain textural effects on the magnetic stability in synthetic, polycrystalline greigite flakes. We demonstrate that these effects stem from inter-grown crystallites with mean coherence length (MCL) of about 20 nm in single-domain magnetic state, which generate modifiable coherent magnetization volume (CMV) configurations in the flakes. At room temperature, the instability of the CVM configuration is exhibited by the angular dependence of the FMR spectra in fields of less than 100 mT and its reset by stronger fields. This finding highlights the magnetic manipulation of polycrystalline greigite, which is a novel trait to detect this mineral phase in Earth systems and to assess its fidelity as paleomagnetic information carrier. Additionally, our magneto-spectroscopic approach to analyse instable CMV opens the door for a new more rigorous magnetic assessment and interpretation of polycrystalline nano-materials.

Polyaramid-Based Flexible Antibacterial Coatings Fabricated Using Laser-Induced Carbonization and Copper Electroplating.

A method for the fabrication of flexible electrical circuits on polyaramid substrates is presented based on laser-induced carbonization followed by copper electroplating. Locally carbonized flexible sheets of polyaramid (Nomex), by laser radiation, create rough and highly porous microstructures that show a higher degree of graphitization than thermally carbonized Nomex sheets. The found recipe for laser-induced carbonization creates conductivities of up to ∼45 S cm-1, thereby exceeding that observed for thermally pyrolyzed materials (∼38 S cm-1) and laser carbon derived from Kapton using the same laser wavelength (∼35 S cm-1). The electrical conductivity of the carbonized tracks was further improved by electroplating with copper. To demonstrate the electrical performance, fabricated circuits were tested and improvement of the sheet resistance was determined. Copper films exhibit antimicrobial activity and were used to fabricate customized flexible antibacterial coatings. The integration of laser carbonization and electroplating technologies in a polyaramid substrate points to the development of customized circuit designs for smart textiles operating in high-temperature environments.

Hysteresis Behavior in the Sorption Equilibrium of Water in Anodes for Li-Ion Batteries.

Hysteresis in the sorption equilibrium influences the production process of many multicomponent material systems. Electrodes for Li-ion batteries consist of several materials, some of which exhibit hysteresis in their sorption equilibrium with water. The moisture content adsorbed and absorbed in the electrodes of the Li-ion battery turned out to be an issue for its electrochemical performance and is reduced in the post-drying process. During this process, hysteresis in the sorption equilibrium needs to be overcome in order to achieve a low residual moisture content of the electrode. Modeling the post-drying process requires a description of the sorption equilibria of water in the components of the battery. This paper builds on previous research about the sorption equilibria and examines the hysteresis behavior of typical graphite anodes, with the active material graphite, carbon black as the conductive additive, and sodium carboxymethyl cellulose as well as styrene butadiene rubber as polymeric binders. Moreover, the mechanisms for the occurrence of hysteresis are presented, and how sorption equilibria during drying can be described is shown by applying models from the literature on the materials of battery electrodes. Theoretical deliberations on hysteresis mechanisms are validated, investigating graphite anodes of different material compositions and their materials.

Liquid-Phase Quasi-Epitaxial Growth of Highly Stable, Monolithic UiO-66-NH2 MOF thin Films on Solid Substrates.

Invited for this month's cover is the group of Dr. Tawheed Hashem from the Karlsruhe Institute of Technology. The cover picture shows a successful synthesis of high quality, monolithic UiO-66-NH2 MOF thin films on diverse solid substrates via a low-temperature liquid phase epitaxy method. The achievement of continuous MOF-coatings with low defect densities and pronounced stability against high temperatures and hot water was proven. The new type of coatings clearly outperforms other reported types of MOF thin films. Read the full text of their Communication at https://doi.org/10.1002/open.201900324.

Liquid-Phase Quasi-Epitaxial Growth of Highly Stable, Monolithic UiO-66-NH2 MOF thin Films on Solid Substrates.

High quality, monolithic UiO-66-NH2 thin films on diverse solid substrates have been prepared via a low temperature liquid phase epitaxy method. The achievement of continuous films with low defect densities and great stability against high temperatures and hot water is proven, clearly outperforming other reported types of MOF thin films.

Facile template-free synthesis of multifunctional 3D cellular carbon from edible rice paper.

Edible rice paper wrapper is found to be an interesting precursor of a porous and light-weight carbon material. During pyrolysis, material samples show significant differences in length change, displaying typical 20-25% shrinking in the in-plane directions, and strongly expanding (up to 500%) across their out-of-plane direction. This results in a template-free synthesis of a 3D network of cellular carbon material. The out-of-plane expansion also allows for fabrication of 3D shapes of cellular carbon material from the 2D precursor. The rice paper derived carbon material features a hierarchical porosity, resulting in a specific surface area ranging from 6 m2 g-1 to 239 m2 g-1 depending on the synthesis temperature. The carbon material has a density of 0.02-0.03 g cm-3, and a higher modulus-density ratio than reported for other cellular carbon materials. It is mechanically stiff and exhibits excellent fire-resistant properties.

Cation diffusion patterns across the magneto-structural transition in Fe7S8.

Migration of atoms in solids during diffusion-dependent reactions is relatively fast and generally not directly recordable in experiments. Here we present an experimental framework that includes fast differential scanning calorimetry to resolve cation-migration paths in crystalline solids using the reversible magneto-structural transition of 4C to 1C pyrrhotite as a testbed. The transition between these two polymorphic Fe7S8 phases at about 600 K is a diffusive process of vacancies, respectively of Fe in octahedral interstitial sites within a hexagonal close-packed lattice of sulfur, and it coincides with the Curie temperature of 4C pyrrhotite. The Fe cations migrate along three kinds of diffusion paths, and their enthalpy contributions to the total reaction enthalpy are taken to define the diffusion patterns in the endothermic reaction and the exothermic back-reaction, respectively. Our experimental findings provide insight into the potential of diffusion patterns to disentangle ordering mechanisms in solids.

Biopebble Containers: DNA-Directed Surface Assembly of Mesoporous Silica Nanoparticles for Cell Studies.

The development of methods for colloidal self-assembly on solid surfaces is important for many applications in biomedical sciences. Toward this goal, described is a versatile class of mesoporous silica nanoparticles (MSN) that contain on their surface various types of DNA molecules to enable their self-assembly into micropatterned surface architectures useful for cell studies. Monodisperse dye-doped MSN are synthesized by biphase stratification and functionalized with an aptamer oligonucleotide that serves as gatekeeper for the triggered release of encapsulated molecular cargo, such as fluorescent dye rhodamine B or the anticancer drug doxorubicin. One or two additional types of oligonucleotides are installed on the MSN surface to enable DNA-directed immobilization on solid substrates bearing patterns of complementary capture oligonucleotides. It is demonstrated that this strategy can be used for efficient self-assembly of microstructured surface architectures, which not only promote the adhesion and guidance of cells but also are capable of affecting the fate of adhered cells through triggered release of their cargo. It is believed that this approach is useful for diverse applications in tissue engineering and nanobio sciences.

MOF-templated synthesis of 3D Bi2O3 supracrystals with bcc packing.

We describe a non-conventional, MOF-based approach with modified linkers to fabricate 3D Bi2O3 supracrystals. The nanoparticle (NP) assembly exhibits bcc-packing, which is difficult to achieve with other methods. The NPs possess a very narrow size distribution. The individual NPs were synthesized inside the pores of a surface-mounted metal-organic framework (SURMOF) template via a photo-decomposition procedure. The supracrystals were thoroughly characterized using X-ray diffraction (XRD), infrared (IR) and Raman spectroscopy as well as high-resolution transmission electron microscopy (HR-TEM) and SAED (Selected Area Electron Diffraction). In order to achieve sharp size distributions of the NPs, the pores within the SURMOF were functionalized with amino (-NH2) functional groups acting as nucleation centers. MOFs lacking such additional functionalities, Cu3(BTC)2, yielded much broader size distributions. These findings provide a unique molecular design tool for creating nanometer-sized reaction compartments for the synthesis of supracrystals with packing types not accessible via self-assembly.

Chemically reprogrammable metal organic frameworks (MOFs) based on Diels-Alder chemistry.

We present the reversible Diels-Alder functionalization of metal organic frameworks (MOFs). Cyclopentadiene (Cp) functional MOFs are ligated with dienophiles to fabricate functional MOFs with a reprogrammable chemical nature. Our strategy thus constitutes an unprecedented concept for chemically dynamic MOFs able to be recoded.

O2 Activation on Ceria Catalysts-The Importance of Substrate Crystallographic Orientation.

An atomic-level understanding of dioxygen activation on metal oxides remains one of the major challenges in heterogeneous catalysis. By performing a thorough surface-science study of all three low-index single-crystal surfaces of ceria, probably the most important redox catalysts, we provide a direct spectroscopic characterization of reactive dioxygen species at defect sites on the reduced ceria (110) and (100) surfaces. Surprisingly, neither of these superoxo and peroxo species was found on ceria (111), the thermodynamically most stable surface of this oxide. Applying density functional theory, we could relate these apparently inconsistent findings to a sub-surface diffusion of O vacancies on (111) substrates, but not on the less-closely packed surfaces. These observations resolve a long standing debate concerning the location of O vacancies on ceria surfaces and the activation of O2 on ceria powders.

Rendering Photoreactivity to Ceria: The Role of Defects.

The photoreactivity of ceria, a photochemically inert oxide with a large band gap, can be increased to competitive values by introducing defects. This previously unexplained phenomenon has been investigated by monitoring the UV-induced decomposition of N2 O on well-defined single crystals of ceria by using infrared reflection-absorption spectroscopy (IRRAS). The IRRAS data, in conjunction with theory, provide direct evidence that reducing the ceria(110) surface yields high photoreactivity. No such effects are seen on the (111) surface. The low-temperature photodecomposition of N2 O occurs at surface O vacancies on the (110) surface, where the electron-rich cerium cations with a significantly lowered coordination number cause a local lowering of the huge band gap (ca. 6 eV). The quantum efficiency of strongly reduced ceria(110) surfaces in the photodecomposition of N2 O amounts to 0.03 %, and is thus comparable to that reported for the photooxidation of CO on rutile TiO2 (110).

Edible solid lipid nanoparticles (SLN) as carrier system for antioxidants of different lipophilicity.

Ferulic acid (FA) and tocopherol (Toc) loaded solid lipid nanoparticles (SLN) were prepared by a hot homogenisation method. The particle size distribution, zeta potential and melting behaviour of the SLN as well as the stability, encapsulation efficiency and radical scavenging activity of FA and Toc in the SLN were analysed. The different formulations containing up to 2.8 mg g-1 of FA or Toc were stable during at least 15 weeks of storage at room temperature. Despite partial degradation and / or release of FA and Toc during storage, significant radical scavenging activity was maintained. DSC measurements and radical scavenging tests after different time periods revealed that the re-structuring of the lipid matrix was connected to the enhanced antioxidant activity of Toc but did not affect the activity of FA.