A new non-interpenetrating 3D metal–organic framework {[Ni₄(μ₆-MTB)₂(μ₂-H₂O)₄(H₂O)₄]·10DMF·11H₂O}_n (DMF = N,N′-dimethylformamide) built from nickel(II) ions as connectors and methanetetrabenzoate ligands (MTB⁴⁻) as linkers has been synthesized and characterized. The single crystal X-ray diffraction showed that complex exhibits CaF₂-like fluorite structure topology and four types of 3D channels with sizes about 12.6 × 9.4 Ų, 9.4 × 8.0 Ų, 12.6 × 11.7 Ų and 14.9 × 14.9 Ų, which are filled with guest molecules. Conditions of the activation of the compound have been studied and optimized by powder X-ray diffraction during in situ heating, thermogravimetric analysis and infrared spectroscopy. Nitrogen and carbon dioxide adsorption showed that the activated sample exhibits a BET specific surface area of 700 m² g⁻¹ and a carbon dioxide uptake of 12.36 wt% at 0 °C, which are the highest values reported for the compounds of the MTB⁴⁻ series. The complex was tested in Knoevenagel condensation of aldehydes and active methylene compounds. Straightforward dependence of the substrate conversion on the size of used aldehyde was established. A possible mechanism of Knoevenagel condensation over a MTB⁴⁻ containing a metal–organic framework was proposed.

The present article intended to study the influence of post-synthetic modification with ethylenediamine (en, diamine) and diethylenetriamine (deta, triamine) within the coordinatively unsaturated sites (CUSs) of HKUST-1 on carbon dioxide and hydrogen storage. The as-sythesized adsorbent was solvent-exchanged and subsequently post-synthetically modified with di-/triamines as sources of amine-based sorption sites due to the increased CO₂ storage capacity. It is known that carbon dioxide molecules have a high affinity for amine groups, and moreover, the volume of amine molecules itself reduces the free pore volume in HKUST-1, which is the driving force for increasing the hydrogen storage capacity. Different concentrations of amines were used for modification of HKUST-1, through which materials with different molar ratios of HKUST-1 to amine: 1:0.05; 1:0.1; 1:0.25; 1:0.5; 1:0.75; 1:1; 1:1.5 were synthesized. Adsorption measurements of carbon dioxide at 0 °C up to 1 bar have shown that the compounds can adsorb large amounts of carbon dioxide. In general, deta-modified samples showed higher adsorbed amounts of CO₂ compared to en-modified materials, which can be explained by the higher number of amine groups within the deta molecule. With an increasing molar ratio of amines, there was a decrease in wt.% CO₂. The maximum storage capacity of CO₂ was 22.3 wt.% for HKUST-1: en/1:0.1 and 33.1 wt.% for HKUST-1: deta/1:0.05 at 0 °C and 1 bar. Hydrogen adsorption measurements showed the same trend as carbon dioxide, with the maximum H₂ adsorbed amounts being 1.82 wt.% for HKUST-1: en/1:0.1 and 2.28 wt.% for HKUST-1: deta/1:0.05 at − 196 °C and 1 bar.