Poly(benzimidazobenzophenanthroline)-Ladder-Type Two-Dimensional Conjugated Covalent Organic Framework for Fast Proton Storage

Electrochemical proton storage plays an essential role in designing next-generation high-rate energy storage devices, e.g., aqueous batteries. Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are promising electrode materials, but their competitive proton and metal-ion insertion mechanisms remain elusive, and proton storage in COFs is rarely explored. Here, we report a perinone-based poly(benzimidazobenzophenanthroline) (BBL)-ladder-type 2D c-COF for fast proton storage in both a mild aqueous Zn-ion electrolyte and strong acid. We unveil that the discharged C−O− groups exhibit largely reduced basicity due to the considerable π-delocalization in perinone, thus affording the 2D c-COF a unique affinity for protons with fast kinetics. As a consequence, the 2D c-COF electrode presents an outstanding rate capability of up to 200 A g−1 (over 2500 C), surpassing the state-of-the-art conjugated polymers, COFs, and metal–organic frameworks. Our work reports the first example of pure proton storage among COFs and highlights the great potential of BBL-ladder-type 2D conjugated polymers in future energy devices

Thiophene-Bridged Donor–Acceptor sp2-Carbon-Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene-bridged donor–acceptor-based 2D sp2-carbon-linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron-accepting building block 2,3,8,9,14,15-hexa(4-formylphenyl) diquinoxalino[2,3-a:2′,3′-c]phenazine (HATN-6CHO) and the first electron-donating linker 2,2′-([2,2′-bithiophene]-5,5′-diyl)diacetonitrile (ThDAN) provides the 2D CCP-HATNThDAN (2D CCP-Th). Compared with the corresponding biphenyl-bridged 2D CCP-HATN-BDAN (2D CCP-BD), the bithiophene-based 2D CCP-Th exhibits a wide light-harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP-Th a promising candidate for PEC water reduction. As a result, 2D CCP-Th presents a superb H2-evolution photocurrent density up to ≈7.9 µA cm−2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm−2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H2. © 2020 The Authors. Advanced Materials published by Wiley-VCH Gmb

Mechanistic insights into the reversible lithium storage in an open porous carbon via metal cluster formation in all solid-state batteries

Porous carbons are promising anode materials for next generation lithium batteries due to their large lithium storage capacities. However, their highsloping capacity during lithiation and delithiation as well as capacity fading due to intense formation of solid electrolyte interphase (SEI) limit their gravimetric and volumetric energy densities. Herein we compare a microporous carbide derived carbon material (MPC) as promising future anode for all solid state batteries with a commercial high performance hard carbon anode. The MPC obtains high and reversible lithiation capacities of 1000 mAh g 1 carbon in half cells exhibiting an extended plateau region near 0 V vs. Li/Liþ preferable for full cell application. The well defined microporosity of the MPC with a specific surface area of >1500 m2 g 1 combines well with the argyrodite type electrolyte (Li6PS5Cl) suppressing extensive SEI formation to deliver high coulombic efficiencies. Preliminary full cell measurements vs. nickel rich NMC cathodes (LiNi0.9Co0.05Mn0.05O2) provide a considerably improved average potential of 3.76 V leading to a projected energy density as high as 449 Wh kg 1 and reversible cycling for more than 60 cycles. 7Li Nuclear Magnetic Resonance spectroscopy was combined with ex situ Small Angle X ray Scattering to elucidate the storage mechanism of lithium inside the carbon matrix. The formation of extended quasi metallic lithium clusters after electrochemical lithiation was revealed

Linked Curriculum – Chemistry: Different from a Virtual University Vernetztes Studium – Chemie: anders als eine virtuelle Universität

Since 1999 the German Federal Ministry of Education and Research has been supporting the lead project 'Vernetztes Studium – Chemie' ('Network for Education – Chemistry'). Sixteen professors and their co-workers from Germany, Switzerland, and the United Kingdom are involved. During a period of five years a novel internet-based modular system will be developed connecting theory and practice of the chemistry basic studies. This new approach will provide the basic chemical knowledge via the use of multimedia methods in the form of browser-based learning modules which are compiled within an integrated educational concept. The students are able to choose different learning levels depending on their knowledge. Potential users are students and lecturers of chemistry and of other branches of study as well as laboratory assistants, pupils and interested people undertaking further studies in chemistry

Solid-state 13^{13}C-NMR spectroscopic determination of sidechain mobilities in zirconium-based metal-organic frameworks

<p>This Dataset contains the raw data contained in the figures of our journal article in <i>Magnetic Resonance</i>: <a href="https://doi.org/10.5194/mr-2023-13">https://doi.org/10.5194/mr-2023-13</a>.</p&gt

Solid-state 13^{13}C-NMR spectroscopic determination of sidechain mobilities in zirconium-based metal-organic frameworks

<p>This Dataset contains the raw data contained in the figures of our journal article in <i>Magnetic Resonance</i>: <a href="https://doi.org/10.5194/mr-2023-13">https://doi.org/10.5194/mr-2023-13</a>.</p&gt

Carbon Adsorbents from Spent Coffee for Removal of Methylene Blue and Methyl Orange from Water

Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed

Electrolyte mobility in supercapacitor electrodes - solid state NMR studies on hierarchical and narrow pore sized carbons

Electrical double layer capacitors are in the special focus of current energy storage research due to their high power density. They store charge physically by quick electrosorption of electrolyte ions on the surface of porous carbon electrodes. However, fundamental insight into the storage mechanism, especially on a molecular level is limited despite of the crucial importance to understand and improve this promising technology. We have investigated and quantified the mobility of electrolyte ions in supercapacitor electrodes by means of solid-state nuclear magnetic resonance (NMR) spectroscopy. We could discriminate between the mobility of cations, anions, and solvent molecules. The exchange of these species between different pore systems as well as between pore system and external bulk environment is studied in detail by NMR spectroscopic methods

Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs)

Nuclear Magnetic Resonance (NMR) spectroscopy is a well-established method for the investigation of various types of porous materials. During the past decade, metal–organic frameworks have attracted increasing research interest. Solid-state NMR spectroscopy has rapidly evolved into an important tool for the study of the structure, dynamics and flexibility of these materials, as well as for the characterization of host–guest interactions with adsorbed species such as xenon, carbon dioxide, water, and many others. The present review introduces and highlights recent developments in this rapidly growing field