Isoreticular Expansion of Metal–Organic Frameworks via Pillaring of Metal Templated Tunable Building Layers: Hydrogen Storage and Selective CO₂ Capture

Abstract

The deliberate construction of isoreticular eea‐metal–organic frameworks (MOFs) (Cu‐eea‐1, Cu‐eea‐2 and Cu‐eea‐3) and rtl‐MOFs (Co‐rtl‐1 and Co‐rtl‐2) has been accomplished based on the ligand‐to‐axial pillaring of supermolecular building layers. The use of different metal ions resulted in two types of supermolecular building layers (SBLs): Kagome (kgm) and square lattices (sql) which further interconnect to form anticipated 3D‐MOFs. The isoreticular expansion of (3,6)‐connected Cu‐MOFs has been achieved with desired eea‐topology based on kgm building layers. In addition, two (3,6)‐connected Co‐rtl‐MOFs were also successfully constructed based on sql building layers. The Cu‐eea‐MOFs were shown to act as hydrogen storage materials with appreciable amount of hydrogen uptake abilities. Moreover Cu‐eea‐MOFs have also exhibited remarkable CO2 capture ability at ambient condition compared to nitrogen and methane, due to the presence of amide functionalities.

V═O Functionalized {Tm2}–Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2 and Oxidation of Mustard Gas

“…The conversion rate at 25 °C varied from 58% to 99% with time from 1 to 4 h, whereas the conversion rate could reach almost 100% within 2 h when the reaction temperature was set at 40 °C. It is worth mentioning that the conversion rate is one more important indicator that reflects the transformation of mustard gas into low-toxicity products of oxidized sulfoxide (CEESO). − Furthermore, blank experiments employing 0.025 mmol of the related raw materials of NUC-11 were conducted at 40 °C over 2 h, as detailed in Table S5. The dramatically decreased conversion rate implied that the synergistic effect of various active species exists in NUC-11 .…”

Engineered Bifunctional Luminescent Pillared‐Layer Frameworks for Adsorption of CO2 and Sensitive Detection of Nitrobenzene in Aqueous Media

“…From a topological point of view, a pillared‐layer MOF is usually composed of 2D metal–carboxylate layered nets and (rigid) linear bis‐pyridyl N‐tethering pillars [19–25] . Hence, the formation of (luminescent) isoreticular pillared‐layer MOFs can be reasonably achieved by applying a dual‐ligand synthetic approach (Scheme 1), [19] which is an alternative and effective approach to generate well‐designed porous frameworks with adjustable pore sizes and tunable structural features by simply adjusting the length of the linear bis‐pyridyl pillars [20–22, 26] or by changing the polycarboxylate moieties [23, 24, 27] . Of particular note, as the length of the bridging ligands is increased, MOFs usually possess network interpenetration, which tends to diminish the porosity [19, 25] .…”

Amide-Functionalized Metal–Organic Frameworks Coupled with Open Fe/Sc Sites for Efficient Acetylene Purification

“…The triangular prismatic [M 3 O­(COO) 6 ] trinuclear cluster formed by the coordination of a single μ 3 -O and three M 2+/3+ is a typical secondary building unit (SBU) in MOFs. − Because of the high symmetry, rich design elements, and flexible coordination environment, it is widely used for adsorption, separation, catalysis, fluorescent sensing, and other fields. Moreover, amide-functionalized metal–organic framework (AFMOF) is widely studied in the field of gas adsorption and separation because of its active O/N sites. , However, as far as we know, few high stability AFMOFs have been used in gas adsorption and separation studies. − Our group has been committed to the structural design and adsorption/separation performance research of the trinuclear cluster MOFs. , Thus, it is attractive and challenging to design and synthesize MOFs with durable and multiple active sites to effectively separate gases.…”

“…Moreover, amide-functionalized metal− organic framework (AFMOF) is widely studied in the field of gas adsorption and separation because of its active O/N sites. 45,46 However, as far as we know, few high stability AFMOFs have been used in gas adsorption and separation studies. 47−49 Our group has been committed to the structural design and adsorption/separation performance research of the Gas Adsorption, Separation, and Breakthrough Experiments.…”