New Supercage Metal–Organic Framework Based on Allopurinol Ligands Showing Acetylene Storage and Separation

Abstract

To develop efficienta dsorbent materials for storage and separation of C 2 H 2 ,a nu nprecedented supercage MOF,[ Me 2 NH 2 ]•[Zn 3 (ALP)(TDC) 2.5 ]•3.5DMF•2 H 2 O(1)w as constructedt hrough medicinal molecule allopurinol (ALP) and S-containing 2,5-thiophenedicarboxylica cid (H 2 TDC). 1 contains an ovel linear trinuclearc luster that is composed by ALP and carboxylates and forms af inal uncommon 5-connected yfy topologicalf ramework. The framework possesses three types of interlinked cages decorated by rich functional sites, and reveals not only high adsorption capacity for C 2 H 2 but also excellent selective separation forC 2 H 2 /CO 2 and C 2 H 2 /CH 4 at 298 K. Dynamic breakthrough experiments on C 2 H 2 /CO 2 (1:1) mixture and C 2 H 2 /CH 4 (1:1) mixture also demonstrated the potential of the materialt os eparate C 2 H 2 from CO 2 or CH 4 mixtures. Molecular simulations were also studied to identify the different CO 2-a nd C 2 H 2-b inding sites in 1,s uch as carboxylate groups, Sa toms and carbonyl groups.

Partial Linker Substitution Strategy to Construct a Quaternary HKUST-like MOF for Efficient Acetylene Storage and Separation

“…11 The total pore volume of FUT-1a was calculated to be 0.65 cm 3 /g, lower than the theoretical value (1.11 cm 3 /g, calculated from the crystal structure), which should be due to the partial occupation of pores by NO 3 − anions leading to partial inaccessibility of pores and the inadequate filling of N 2 on irregular pore surfaces. 24,25 The pore size distribution obtained by applying the 273 K CO 2 and 77 K N 2 isotherms based on the NLDFT model show that there are narrow pores at 5.7, 8.3, and 11.8 Å (Figure 3b), which are close to the cavity sizes observed in the crystal structure.…”

“…The corresponding Brunauer–Emmett–Teller surface areas and Langmuir surface areas are estimated to be 1522 and 1821 m 2 /g (Figure S7), respectively, which are relatively moderate in comparison to those of the tbo topology MOF such as ZJU-35a (2899 m 2 /g) and Cu-tbo-MOF-5 (3971 m 2 /g) but slightly higher than the prototypical HKUST-1 (1401 m 2 /g) . The total pore volume of FUT-1a was calculated to be 0.65 cm 3 /g, lower than the theoretical value (1.11 cm 3 /g, calculated from the crystal structure), which should be due to the partial occupation of pores by NO 3 – anions leading to partial inaccessibility of pores and the inadequate filling of N 2 on irregular pore surfaces. , The pore size distribution obtained by applying the 273 K CO 2 and 77 K N 2 isotherms based on the NLDFT model show that there are narrow pores at 5.7, 8.3, and 11.8 Å (Figure b), which are close to the cavity sizes observed in the crystal structure.…”

Fused aza-heterocyclic ligands: expanding the MOF chemist's toolbox

“…The metal coordination in ALP-MOF-1 and 2 relates to that previously observed by Zhu with the same allopurinol ligand and 2,5-thiophenedicarboxylic acid as a co-ligand. 54 In that case, a similar threefold-capping of a polynuclear cluster node was observed from the L10 ligand, but only on a single face with the remaining coordination sites occupied by carboxylate groups. As such, the cluster nuclearity was limited to three zinc ions, with dimethylammonium cations present for charge balance.…”

An Isomeric Copper‐Diisophthalate Framework Platform for Storage and Purification of C2H2and Exploration of the Positional Effect of the Methyl Group

“…As shown in Figure 3e and Figure 3f, the hierarchy of adsorption selectivity did not change when the C 2 H 2 molar ratio in gas mixtures changed from 0.1 to 0.9. It is noteworthy that among the three MOF compounds, ZJNU‐96 showed the highest C 2 H 2 /CH 4 and C 2 H 2 /CO 2 adsorption selectivities at 298 K and 1 atm, which is comparable to that of its parent MOF NOTT‐101 (C 2 H 2 /CH 4 : 26.7), [16] but higher than those of some other reported MOFs such as BUT‐70B (C 2 H 2 /CH 4 : 23.3), [41] PCM‐48 (C 2 H 2 /CH 4 : 23.3), [42] UTSA‐222 (C 2 H 2 /CH 4 : 19), [43] FJU‐36 (C 2 H 2 /CH 4 : 17.7), [44] UPC‐33 (C 2 H 2 /CH 4 : 7.78), [45] ZJNU‐15 (C 2 H 2 /CO 2 : 4.4), [11b] Cu(BDC‐Br) (C 2 H 2 /CO 2 : 3.9), [46] NTU‐9 (C 2 H 2 /CO 2 : 3.5), [47] BSF‐1 (C 2 H 2 /CO 2 : 3.3), [48] ZJNU‐14 (C 2 H 2 /CO 2 : 3.42), [17b] UTSA‐68 (C 2 H 2 /CO 2 : 3.4), [49] Zn 3 (ALP)(TDC) 2.5 (C 2 H 2 /CO 2 : 2.8), [50] and Co(btzip)(H 2 btzip) (C 2 H 2 /CO 2 : 2.5) [51] at the same conditions. In particular, the C 2 H 2 /CH 4 and C 2 H 2 /CO 2 adsorption selectivity of the ortho ‐dimethyl‐functionalized MOF ZJNU‐96 is 8.6 % and 8.3 % higher than the meta ‐dimethyl‐decorated counterpart ZJNU‐95 .…”