Fluorinated Benzimidazole-Linked Highly Conjugated Polymer Enabling Covalent Polysulfide Anchoring for Stable Sulfur Batteries.

Sulfur is one of the most abundant and economical elements in the p-block family and highly redox active, potentially utilizable as a charge-storing electrode with high theoretical capacities. However, its inherent good solubility in many electrolytes inhibits its accessibility as an electrode material in typical metal-sulfur batteries. In this work, the synthetically designed fluorinated porous polymer, when treated with elemental sulfur through a well-known nucleophilic aromatic substitution mechanism (SN Ar), allows for the covalent integration of polysulfides into a highly conjugated benzimidazole polymer by replacing the fluorine atoms. Chemically robust benzimidazole linkages allow such harsh post-synthetic treatment and facilitate the electronic activation of the anchored polysulfides for redox reactions under applied potential. The electrode amalgamated with sulfurized polymer mitigates the so-called polysulfide shuttle effect in the lithium-sulfur (Li-S) battery and also enables a reversible, more environmentally friendly, and more economical aluminum-sulfur (Al-S) battery that is configured with mostly p-block elements as cathode, anode, and electrolytes. The improved cycling stabilities and reduction of the overpotential in both cases pave the way for future sustainable energy storage solutions.

An Alkyne-Bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture.

The high degree of corrosivity and reactivity of bromine, which is released from various sources, poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π-electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6 g g-1) over iodine by ~41 % shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

High-field and fast-spinning 1H MAS NMR spectroscopy for the characterization of two-dimensional covalent organic frameworks.

Two-dimensional (2D) materials, like 2D covalent organic frameworks (COFs), have been attracting increasing research interest. They are usually obtained as polycrystalline powders. Solid-state NMR spectroscopy is capable of delivering structural information about such materials. Previous studies have applied, for example, 13C cross-polarization magic angle spinning (CP MAS) NMR experiments to characterize 2D COFs. Herein, we demonstrate the usefulness of high-field and fast-spinning 1H MAS NMR spectroscopy to resolve and quantify the signals of different 1H species within 2D COFs, including the edge sites and/or defects. Moreover, 1H-13C heteronuclear correlation (HETCOR) spectroscopy has also been applied and can provide improved resolution to obtain further information about stacking effects as well as edge sites/defects.

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes.

Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

The Dilemma of Reproducibility of Gating Isotherms for Flexible MOFs.

Porous materials receive a high level of scientific and technological interest due to their applications in various fields such as adsorption, separation and storage, catalysis, ion exchange, nanotechnology, etc. Gas adsorption is a well-established tool for the characterization of the texture of porous solids. Physisorption isotherms are generally expected to be well reproducible for rigid adsorbents, but this is not always the case for nonrigid (flexible) materials. The presence of a metastability region and sensitivity of the activation barriers to the material's texture often influence the isotherms' run. Here, we address the complexity that arises in terms of reproducibility and sample handling for flexible metal-organic frameworks, with the example of DUT-8(Ni). It belongs to the group of "gate opening" metal-organic frameworks and is a typical representative of the pillared layer compounds. We propose characteristic parameters for the analysis and comparison of adsorption isotherms, showing the "gate opening" step, associated with the adsorption-induced solid-state phase transition. A set of 50 nitrogen physisorption isotherms measured at 77 K were analyzed and correlated with the synthetic and outgassing conditions. The study highlights the importance of accurate descriptions and record-keeping of experimental details and their role in the replication of scientific results.

Amplification of negative gas adsorption in a multivariate framework.

The approach of employing multivariate MOFs was used to fine-tune the mechanical properties of the flexible framework DUT-49. In situ XRD, NMR and physisorption studies showed that the partial incorporation of a more rigid linker into the DUT-49 framework enables stabilization of the metastable open pore phase, which led to a two-fold amplification of the expelled gas amount upon the "negative gas adsorption" transition.

Sulfide-Bridged Covalent Quinoxaline Frameworks for Lithium-Organosulfide Batteries.

The chelating ability of quinoxaline cores and the redox activity of organosulfide bridges in layered covalent organic frameworks (COFs) offer dual active sites for reversible lithium (Li)-storage. The designed COFs combining these properties feature disulfide and polysulfide-bridged networks showcasing an intriguing Li-storage mechanism, which can be considered as a lithium-organosulfide (Li-OrS) battery. The experimental-computational elucidation of three quinoxaline COFs containing systematically enhanced sulfur atoms in sulfide bridging demonstrates fast kinetics during Li interactions with the quinoxaline core. Meanwhile, bilateral covalent bonding of sulfide bridges to the quinoxaline core enables a redox-mediated reversible cleavage of the sulfursulfur bond and the formation of covalently anchored lithium-sulfide chains or clusters during Li-interactions, accompanied by a marked reduction of Li-polysulfide (Li-PS) dissolution into the electrolyte, a frequent drawback of lithium-sulfur (Li-S) batteries. The electrochemical behavior of model compounds mimicking the sulfide linkages of the COFs and operando Raman studies on the framework structure unravels the reversibility of the profound Li-ion-organosulfide interactions. Thus, integrating redox-active organic-framework materials with covalently anchored sulfides enables a stable Li-OrS battery mechanism which shows benefits over a typical Li-S battery.

Solid-state NMR insights into alcohol adsorption by metal-organic frameworks: adsorption state, selectivity, and adsorption-induced phase transitions.

Alcohol adsorption by metal-organic frameworks (ZIF-8 and ZIF-11) in aqueous solutions is investigated including alcohol mixtures. Solid-state 13C NMR spectroscopy is demonstrated to be well-suited for such liquid-phase adsorption studies at the molecular level. Adsorption-induced immobilization could be visualized. Finally, an unexpected phase transition of ZIF-11 was discovered.

Sustainable Protein-Based Binder for Lithium-Sulfur Cathodes Processed by a Solvent-Free Dry-Coating Method.

In the market for next-generation energy storage, lithium-sulfur (Li-S) technology is one of the most promising candidates due to its high theoretical specific energy and cost-efficient ubiquitous active materials. In this study, this cell system was combined with a cost-efficient sustainable solvent-free electrode dry-coating process (DRYtraec®). So far, this process has been only feasible with polytetrafluoroethylene (PTFE)-based binders. To increase the sustainability of electrode processing and to decrease the undesired fluorine content of Li-S batteries, a renewable, biodegradable, and fluorine-free polypeptide was employed as a binder for solvent-free electrode manufacturing. The yielded sulfur/carbon dry-film cathodes were electrochemically evaluated under lean electrolyte conditions at coin and pouch cell level, using the state-of-the-art 1,2-dimethoxyethane/1,3-dioxolane electrolyte (DME/DOL) as well as the sparingly polysulfide-solvating electrolytes hexylmethylether (HME)/DOL and tetramethylene sulfone/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TMS/TTE). These results demonstrated that the PTFE binder can be replaced by the biodegradable sericin as the cycle stability and performance of the cathodes was retained.