MXenes, an emerging class of conductive two-dimensional materials, have been regarded as promising candidates in the field of electrochemical energy storage. The electrochemical performance of their representative TiC T , where T represents the surface termination group of F, O, or OH, strongly relies on termination-mediated surface functionalization, but an in-depth understanding of the relationship between them remains unresolved. Here, we studied comprehensively the structural feature and electrochemical performance of two kinds of TiC T MXenes obtained by etching the TiAlC precursor in aqueous HF solution at low concentration (6 mol/L) and high concentration of (15 mol/L). A significantly higher capacitance was recognized in a low-concentration HF-etched MXene (TiC T -6M) electrode. In situ Raman spectroscopy and X-ray photoelectron spectroscopy demonstrate that TiC T -6M has more components of the -O functional group. In combination with X-ray diffraction analysis, low-fieldH nuclear magnetic resonance spectroscopy in terms of relaxation time unambiguously underlines that TiC T -6M is capable of accommodating more high-mobility HO molecules between the TiC T interlayers, enabling more hydrogen ions to be more readily accessible to the active sites of TiC T -6M. The two main key factors ( i.e., high content of -O functional groups that are involved bonding/debonding-induced pseudocapacitance and more high-mobility water intercalated between the MXene interlayers) simultaneously account for the superior capacitance of the TiC T -6M electrode. This study provides a guideline for the rational design and construction of high-capacitance MXene and MXene-based hybrid electrodes in aqueous electrolytes.

Developing new materials for the fabrication of proton exchange membranes (PEMs) for fuel cells is of great significance. Herein, a series of highly crystalline, porous, and stable new covalent organic frameworks (COFs) have been developed by a stepwise synthesis strategy. The synthesized COFs exhibit high hydrophilicity and excellent stability in strong acid or base (e.g., 12 m NaOH or HCl) and boiling water. These features make them ideal platforms for proton conduction applications. Upon loading with H3PO4, the COFs (H3PO4@COFs) realize an ultrahigh proton conductivity of 1.13×10−1 S cm−1, the highest among all COF materials, and maintain high proton conductivity across a wide relative humidity (40–100 %) and temperature range (20–80 °C). Furthermore, membrane electrode assemblies were fabricated using H3PO4@COFs as the solid electrolyte membrane for proton exchange resulting in a maximum power density of 81 mW cm−2 and a maximum current density of 456 mA cm−2, which exceeds all previously reported COF materials.

No abstract

Green synthesis of crystalline porous materials for energy-related applications is of great significance but very challenging. Here, we create a green strategy to fabricate a highly crystalline olefin-linked pyrazine-based covalent organic framework (COF) with high robustness and porosity under solvent-free conditions. The abundant nitrogen sites, high hydrophilicity, and well-defined one-dimensional nanochannels make the resulting COF an ideal platform to confine and stabilize the H3PO4 network in the pores through hydrogen-bonding interactions. The resulting material exhibits low activation energy (Ea) of 0.06 eV, and ultrahigh proton conductivity across a wide relative humidity (10–90 %) and temperature range (25–80 °C). A realistic proton exchange membrane fuel cell using the olefin-linked COF as the solid electrolyte achieve a maximum power of 135 mW cm−2 and a current density of 676 mA cm−2, which exceeds all reported COF materials.

The emergence of all‐organic frameworks is of fundamental significance, and designing such structures for anion conduction holds great promise in energy conversion and storage applications. Herein, inspired by the efficient anion transport within organisms, a de novo design of covalent organic frameworks (COFs) toward ultrafast anion transport is demonstrated. A phase‐transfer polymerization process is developed to acquire dense and ordered alignment of quaternary ammonium‐functionalized side chains along the channels within the frameworks. The resultant self‐standing COFs membranes exhibit one of the highest hydroxide conductivities (212 mS cm−1 at 80 °C) among the reported anion exchange membranes. Meanwhile, it is found that shorter, more hydrophilic side chains are favorable for anion conduction. The present work highlights the prospects of all‐organic framework materials as the platform building blocks in designing ion exchange membranes and ion sieving membranes.