Enhanced Benzene Adsorption in Chloro-Functionalized Metal-Organic Frameworks.

The functionalization of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalized with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g-1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy, and inelastic neutron scattering, coupled with density functional theory modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by -CH···Cl and Cl···π interactions in porous materials.

Promoting Preferential Zn (002) Deposition with a Low-Concentration Electrolyte Additive for Highly Reversible Zn-Ion Batteries.

Aqueous zinc-ion batteries have promising potential as energy storage devices due to their low cost and environmental friendliness. However, their development has been hindered by zinc dendrite formation and parasitic side reactions. Herein, we introduce a low-concentration sodium benzoate (NaBZ) electrolyte additive to stabilize the electrode-electrolyte interface and promote deposition on the Zn (002) crystal plane. From experimental characterization and computational analyses, NaBZ was found to adsorb on the Zn surface and inhibit side reactions while guiding homogeneous Zn deposition on the (002) plane. Consequently, Zn|Zn symmetric cells with the NaBZ additive cycled stably for over 1000 h at a current density of 0.5 mA cm-2 and an areal capacity of 0.5 mAh cm-2, while Zn|Cu cells showed excellent reversibility with a Coulombic efficiency of 99.05%. Moreover, Zn|Na0.33V2O5 full cells achieve a high specific capacity of 124 mAh g-1 while cycling for 600 h at 2 A g-1. These findings present a low-cost electrolyte modification strategy for reversible zinc-ion batteries.

Switching Adsorbent Layered Material that Enables Stepwise Capture of C8 Aromatics via Single-Crystal-to-Single-Crystal Transformations.

Separation of the C8 aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C8 selectivity. Herein, we report the mixed-linker square lattice (sql) coordination network [Zn2(sba)2(bis)]n·mDMF (sql-4,5-Zn, H2sba or 4 = 4,4'-sulfonyldibenzoic acid, bis or 5 = trans-4,4'-bis(1-imidazolyl)stilbene) and its C8 sorption properties. sql-4,5-Zn was found to exhibit high uptake capacity for liquid C8 aromatics (∼20.2 wt %), and to the best of our knowledge, it is the first sorbent to exhibit selectivity for PX, EB, and MX over OX for binary, ternary, and quaternary mixtures from gas chromatography. Single-crystal structures of narrow-pore, intermediate-pore, and large-pore phases provided insight into the phase transformations, which were enabled by flexibility of the linker ligands and changes in the square grid geometry and interlayer distances. This work adds to the library of two-dimensional coordination networks that exhibit high uptake, thanks to clay-like expansion, and strong selectivity, thanks to shape-selective binding sites, for C8 isomers.

V2O5 Nanospheres with Mixed Vanadium Valences as High Electrochemically Active Aqueous Zinc-Ion Battery Cathode.

A V4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor, and its zinc-ion storage performance was evaluated. The products are hollow spheres consisting of nanoflakes. The V4+-V2O5 cathode exhibits a prominent cycling performance, with a specific capacity of 140 mAh g-1 after 1000 cycles at 10 A g-1, and an excellent rate capability. The good electrochemical performance is attributed to the presence of V4+, which leads to higher electrochemical activity, lower polarization, faster ion diffusion, and higher electrical conductivity than V2O5 without V4+. This engineering strategy of valence state manipulation may pave the way for designing high-performance cathodes for elucidating advanced battery chemistry.