Exceptional capture of methane at low pressure by an iron-based metal-organic framework.

The selective capture of methane (CH4) at low concentrations and its separation from N2 are extremely challenging owing to the weak host-guest interactions between CH4 molecules and any sorbent material. Here, we report the exceptional adsorption of CH4 at low pressure and the efficient separation of CH4/N2 by MFM-300(Fe). MFM-300(Fe) shows a very high uptake for CH4 of 0.85 mmol g-1 at 1 mbar and 298 K and a record CH4/N2 selectivity of 45 for porous solids, representing a new benchmark for CH4 capture and CH4/N2 separation. The excellent separation of CH4/N2 by MFM-300(Fe) has been confirmed by dynamic breakthrough experiments. In situ neutron powder diffraction, and solid-state nuclear magnetic resonance and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modelling, reveal a unique and strong binding of CH4 molecules involving Fe-OH⋯CH4 and C⋯phenyl ring interactions within the pores of MFM-300(Fe), thus promoting the exceptional adsorption of CH4 at low pressure.

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.

Control of evolution of porous copper-based metal-organic materials for electroreduction of CO2 to multi-carbon products.

Electrochemcial reduction of CO2 to multi-carbon (C2+) products is an important but challenging task. Here, we report the control of structural evolution of two porous Cu(ii)-based materials (HKUST-1 and CuMOP, MOP = metal-organic polyhedra) under electrochemical conditions by adsorption of 7,7,8,8-tetracyanoquinodimethane (TNCQ) as an additional electron acceptor. The formation of Cu(i) and Cu(0) species during the structural evolution has been confirmed and analysed by powder X-ray diffraction, and by EPR, Raman, XPS, IR and UV-vis spectroscopies. An electrode decorated with evolved TCNQ@CuMOP shows a selectivity of 68% for C2+ products with a total current density of 268 mA cm-2 and faradaic efficiency of 37% for electrochemcial reduction of CO2 in 1 M aqueous KOH electrolyte at -2.27 V vs. RHE (reversible hydrogen electrode). In situ electron paramagnetic resonance spectroscopy reveals the presence of carbon-centred radicals as key reaction intermediates. This study demonstrates the positive impact of additional electron acceptors on the structural evolution of Cu(ii)-based porous materials to promote the electroreduction of CO2 to C2+ products.

Organic-Inorganic Hybrid Cathode with Dual Energy-Storage Mechanism for Ultrahigh-Rate and Ultralong-Life Aqueous Zinc-Ion Batteries.

The exploitation of cathode materials with high capacity as well as high operating voltage is extremely important for the development of aqueous zinc-ion batteries (ZIBs). Yet, the classical high-capacity materials (e.g., vanadium-based materials) provide a low discharge voltage, while organic cathodes with high operating voltage generally suffer from a low capacity. In this work, organic (ethylenediamine)-inorganic (vanadium oxide) hybrid cathodes, that is, EDA-VO, with a dual energy-storage mechanism, are designed for ultrahigh-rate and ultralong-life ZIBs. The embedded ethylenediamine (EDA) can not only increase the layer spacing of the vanadium oxide, with improved mobility of Zn ions in the V-O layered structure, but also act as a bidentate chelating ligand participating in the storage of Zn ions. This hybrid provides a high specific capacity (382.6 mA h g-1 at 0.5 A g-1 ), elevated voltage (0.82 V) and excellent long-term cycle stability (over 10 000 cycles at 5 A g-1 ). Assistant density functional theory (DFT) calculations indicate the cathode has remarkable electronic conductivity, with an ultralow diffusion barrier of 0.78 eV for an optimal Zn-ion diffusion path in the EDA-VO. This interesting idea of building organic-inorganic hybrid cathode materials with a dual energy-storage mechanism opens a new research direction toward high-energy secondary batteries.

Oxygen Defects in ß-MnO2 Enabling High-Performance Rechargeable Aqueous Zinc/Manganese Dioxide Battery.

Rechargeable aqueous Zn/manganese dioxide (Zn/MnO2) batteries are attractive energy storage technology owing to their merits of low cost, high safety, and environmental friendliness. However, the ß-MnO2 cathode is still plagued by the sluggish ion insertion kinetics due to the relatively narrow tunneled pathway. Furthermore, the energy storage mechanism is under debate as well. Here, ß-MnO2 cathode with enhanced ion insertion kinetics is introduced by the efficient oxygen defect engineering strategy. Density functional theory computations show that the ß-MnO2 host structure is more likely for H+ insertion rather than Zn2+, and the introduction of oxygen defects will facilitate the insertion of H+ into ß-MnO2. This theoretical conjecture is confirmed by the capacity of 302 mA h g-1 and capacity retention of 94% after 300 cycles in the assembled aqueous Zn/ß-MnO2 cell. These results highlight the potentials of defect engineering as a strategy of improving the electrochemical performance of ß-MnO2 in aqueous rechargeable batteries.

Investigation of V2O5 as a low-cost rechargeable aqueous zinc ion battery cathode.

Rechargeable aqueous zinc ion batteries (ZIBs) are highly desirable for large-scale energy storage due to their advantages of safety and low-cost. Development of advanced cathodes for use in aqueous ZIBs is urgently needed. Herein, we report a low-cost rechargeable aqueous Zn-V2O5 cell with 3 M ZnSO4 electrolyte that demonstrates high zinc storage capability. We also investigated the effect of different types/concentrations of the aqueous electrolytes on the performance of the Zn-V2O5 cells.