In this study, we explore the mechanical treatment of two metal-organic frameworks (MOFs), HKUST-1 and MOF-76, applying various milling methods to assess their impact on stability, porosity, and CO2 adsorption capacity. The effects of different mechanical grinding techniques, such as high-energy ball milling and hand grinding, on these MOFs were compared. The impact of milling time, milling speed and ball size during high-energy ball milling was assessed via the Design of Experiments methodology, namely using a 33 Taguchi orthogonal array. The results highlight a marked improvement in CO2 adsorption capacity for HKUST-1 through hand milling, increasing from an initial 25.70 wt.% (5.84 mmol g-1) to 41.37 wt.% (9.40 mmol g-1), marking a significant 38% increase. In contrast, high-energy ball milling seems to worsen this property, diminishing the CO2 adsorption abilities of the materials. Notably, MOF-76 shows resistance to hand grinding, closely resembling the original sample's performance. Hand grinding also proved to be well reproducible. These findings clarify the complex effects of mechanical milling on MOF materials, emphasising the necessity of choosing the proper processing techniques to enhance their stability, texture, and performance in CO2 capture and storage applications.

• Klíčová slova
• Carbon dioxide storage, HKUST-1/MOF-76, Mechanical activation, Metal–organic frameworks, Nitrogen adsorption, Particle size,
• Publikační typ
• časopisecké články MeSH

Due to the increasing demand for energy storage devices, the development of high-energy density batteries is very necessary. Lithium-sulfur (Li-S) batteries have gained wide interest due to their particularly high-energy density. However, even this type of battery still needs to be improved. Novel Cu(II)-based metal-organic framework STAM-1 was synthesized and applied as a composite cathode material as a sulfur host in the lithium-sulfur battery with the aim of regulating the redox kinetics of sulfur cathodes. Prepared STAM-1 was characterized by infrared spectroscopy at ambient temperature and after in-situ heating, elemental analysis, X-ray photoelectron spectroscopy and textural properties by nitrogen and carbon dioxide adsorption at - 196 and 0 °C, respectively. Results of the SEM showed that crystals of STAM-1 created a flake-like structure, the surface was uniform and porous enough for electrolyte and sulfur infiltration. Subsequently, STAM-1 was used as a sulfur carrier in the cathode construction of a Li-S battery. The charge/discharge measurements of the novel S/STAM-1/Super P/PVDF cathode demonstrated the initial discharge capacity of 452 mAh g-1 at 0.5 C and after 100 cycles of 430 mAh g-1, with Coulombic efficiency of 97% during the whole cycling procedure at 0.5 C. It was confirmed that novel Cu-based STAM-1 flakes could accelerate the conversion of sulfur species in the cathode material.

• Klíčová slova
• Cathode materials, Energy storage, Lithium–sulfur battery, Metal–organic framework,
• Publikační typ
• časopisecké články MeSH

CO2 capture via physical adsorption on activated porous carbons represents a promising solution towards effective carbon emission mitigation. Additionally, production costs can be further decreased by utilising biomass as the main precursor and applying energy-efficient activation. In this work, we developed novel cellulose-based activated carbons modified with amines (diethylenetriamine (DETA), 1,2-bis(3-aminopropylamino)ethane (BAPE), and melamine (MELA)) with different numbers of nitrogen atoms as in situ N-doping precursors. We investigated the effect of hydrothermal and thermal activation on the development of their physicochemical properties, which significantly influence the resulting CO2 adsorption capacity. This process entailed an initial hydrothermal activation of biomass precursor and amines at 240 °C, resulting in C+DETA, C+BAPE and C+MELA materials. Thermal samples (C+DETA (P), C+BAPE (P), and C+MELA (P)) were synthesised from hydrothermal materials by subsequent KOH chemical activation and pyrolysis in an inert argon atmosphere. Their chemical and structural properties were characterised using elemental analysis (CHN), infrared spectroscopy (IR), scanning electron microscopy (SEM), and thermogravimetric analysis (TG). The calculated specific surface areas (SBET) for thermal products showed higher values (998 m2 g-1 for C+DETA (P), 1076 m2 g-1 for C+BAPE (P), and 1348 m2 g-1 for C+MELA (P)) compared to the hydrothermal products (769 m2 g-1 for C+DETA, 833 m2 g-1 for C+BAPE, and 1079 m2 g-1 for C+MELA). Carbon dioxide adsorption as measured by volumetric and gravimetric methods at 0 and 25 °C, respectively, showed the opposite trend, which can be attributed to the reduced content of primary adsorption sites in the form of amine groups in thermal products. N2 and CO2 adsorption measurements were carried out on hydrothermal (C) and pyrolysed cellulose (C (P)), which showed a several-fold reduction in adsorption properties compared to amine-modified materials. The recyclability of C+MELA, which showed the highest CO2 adsorption capacity (7.34 mmol g-1), was studied using argon purging and thermal regeneration over five adsorption/desorption cycles.

• Klíčová slova
• amines, carbon dioxide storage, cellulose, hydrothermal synthesis, pyrolysis,
• Publikační typ
• časopisecké články MeSH

Two new alkaline earth metal-organic frameworks (AE-MOFs) containing Sr(II) (UPJS-15) or Ba(II) (UPJS-16) cations and extended tetrahedral linker (MTA) were synthesized and characterized in detail (UPJS stands for University of Pavol Jozef Safarik). Single-crystal X-ray analysis (SC-XRD) revealed that the materials are isostructural and, in their frameworks, one-dimensional channels are present with the size of ~11 × 10 Å2. The activation process of the compounds was studied by the combination of in situ heating infrared spectroscopy (IR), thermal analysis (TA) and in situ high-energy powder X-ray diffraction (HE-PXRD), which confirmed the stability of compounds after desolvation. The prepared compounds were investigated as adsorbents of different gases (Ar, N2, CO2, and H2). Nitrogen and argon adsorption measurements showed that UPJS-15 has SBET area of 1321 m2 g-1 (Ar) / 1250 m2 g-1 (N2), and UPJS-16 does not adsorb mentioned gases. From the environmental application, the materials were studied as CO2 adsorbents, and both compounds adsorb CO2 with a maximum capacity of 22.4 wt.% @ 0 °C; 14.7 wt.% @ 20 °C and 101 kPa for UPJS-15 and 11.5 wt.% @ 0°C; 8.4 wt.% @ 20 °C and 101 kPa for UPJS-16. According to IAST calculations, UPJS-16 shows high selectivity (50 for CO2/N2 10:90 mixture and 455 for CO2/N2 50:50 mixture) and can be applied as CO2 adsorbent from the atmosphere even at low pressures. The increased affinity of materials for CO2 was also studied by DFT modelling, which revealed that the primary adsorption sites are coordinatively unsaturated sites on metal ions, azo bonds, and phenyl rings within the MTA linker. Regarding energy storage, the materials were studied as hydrogen adsorbents, but the materials showed low H2 adsorption properties: 0.19 wt.% for UPJS-15 and 0.04 wt.% for UPJS-16 @ -196 °C and 101 kPa. The enhanced CO2/H2 selectivity could be used to scavenge carbon dioxide from hydrogen in WGS and DSR reactions. The second method of applying samples in the area of energy storage was the use of UPJS-15 as an additive in a lithium-sulfur battery. Cyclic performance at a cycling rate of 0.2 C showed an initial discharge capacity of 337 mAh g-1, which decreased smoothly to 235 mAh g-1 after 100 charge/discharge cycles.

• Klíčová slova
• alkaline earth metals, energy storage, gas adsorption/separation, lithium-sulphur battery, metal–organic frameworks,
• Publikační typ
• časopisecké články MeSH