MXenes with ordered triatomic-layer borate polyanion terminations.

Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO2- species, which cap the MXene surface with an O-B-O configuration. In contrast to conventional chlorine/oxygen-terminated Nb2C with localized charge transport, OBO-terminated Nb2C features band transport described by the Drude model, exhibiting a 15-fold increase in electrical conductivity and a 10-fold improvement in charge mobility at the d.c. limit. This transition is attributed to surface ordering that effectively mitigates charge carrier backscattering and trapping. Additionally, OBO terminations provide Ti3C2 MXene with substantially enriched Li+-hosting sites and thereby a large charge-storage capacity of 420 mAh g-1. Our findings illustrate the potential of intricate termination configurations in MXenes and their applications for (opto)electronics and energy storage.

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.

Redox-Active Metaphosphate-Like Terminals Enable High-Capacity MXene Anodes for Ultrafast Na-Ion Storage.

2D transition metal carbides and/or nitrides, so-called MXenes, are noted as ideal fast-charging cation-intercalation electrode materials, which nevertheless suffer from limited specific capacities. Herein, it is reported that constructing redox-active phosphorus-oxygen terminals can be an attractive strategy for Nb4 C3 MXenes to remarkably boost their specific capacities for ultrafast Na+ storage. As revealed, redox-active terminals with a stoichiometric formula of PO2 - display a metaphosphate-like configuration with each P atom sustaining three PO bonds and one PO dangling bond. Compared with conventional O-terminals, metaphosphate-like terminals empower Nb4 C3 (denoted PO2 -Nb4 C3 ) with considerably enriched carrier density (fourfold), improved conductivity (12.3-fold at 300 K), additional redox-active sites, boosted Nb redox depth, nondeclined Na+ -diffusion capability, and buffered internal stress during Na+ intercalation/de-intercalation. Consequently, compared with O-terminated Nb4 C3 , PO2 -Nb4 C3 exhibits a doubled Na+ -storage capacity (221.0 mAh g-1 ), well-retained fast-charging capability (4.9 min at 80% capacity retention), significantly promoted cycle life (nondegraded capacity over 2000 cycles), and justified feasibility for assembling energy-power-balanced Na-ion capacitors. This study unveils that the molecular-level design of MXene terminals provides opportunities for developing simultaneously high-capacity and fast-charging electrodes, alleviating the energy-power tradeoff typical for energy-storage devices.