Incorporation of bifunctional aminopyridine into an NbO-type MOF for the markedly enhanced adsorption of CO₂ and C₂H₂ over CH₄

Abstract

An NbO-type MOF based on an aminopyridine-heterobifunctionalized diisophthalate linker was synthesized, displaying markedly enhanced C2H2 and CO2 adsorption over CH4 compared to its parent compound.

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

“…To investigate the capturep erformance of 1 for CO 2 ,C 2 H 2 and CH 4 ,g as adsorption was further measured at room temperature. For three gases, 1 displays the most loading for C 2 H 2 but the least loading for CH 4 (Figures 3b and c). The adsorption amounts for C 2 H 2 ,C O 2 and CH 4 under 1a tm are 96.6, 74.5 and 19.5 cm 3 g À1 at 273 K, and 68.6, 44.8 and 10.8 cm 3 g À1 at 298 K, respectively.T he amount of C 2 H 2 is comparable with the most reported valuesi nM OFs (Table S3), but much higher than those of ZJNU-62 [40] and (Me 2 NH 2 ) 2 [Zn 6 (TBAPy) 2 (Ade) 4 (m 4 -O)].…”

“…[1,2] C 2 H 2 is produced primarily from methane( CH 4 )t hermal pyrolysis or hydrocarbon cracking, whichu sually coexists with some carbond ioxide (CO 2 )a nd CH 4 molecules. [3][4][5] This fact makes the separation of C 2 H 2 from C 2 H 2 and CO 2 or C 2 H 2 and CH 4 very importanti nC 2 H 2 industry.C urrent C 2 H 2 separation technology mainly relieso nt raditional refrigerant distillation. But for C 2 H 2 and CO 2 ,d ue to close boilingp oints (C 2 H 2 189.3 K, CO 2 194.7 K), almoste qual size (3.3 3.3 5.7 3 for C 2 H 2 and 3.2 3.3 5.4 3 for CO 2 )a nd identical linear shape, [6,7] the cost and energy consumptionof distillation method are very high.…”

“…Acetylene (C 2 H 2 ) is a raw material for not only many chemical products such as acrylic acid, polyurethane and acetylene alcohol, but also for oxyacetylene cutting in metal manufacturing [1, 2] . C 2 H 2 is produced primarily from methane (CH 4 ) thermal pyrolysis or hydrocarbon cracking, which usually coexists with some carbon dioxide (CO 2 ) and CH 4 molecules [3–5] . This fact makes the separation of C 2 H 2 from C 2 H 2 and CO 2 or C 2 H 2 and CH 4 very important in C 2 H 2 industry.…”

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

“…[11d,40] 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-dimethylfunctionalized MOF ZJNU-96 is 8.6 % and 8.3 % higher than the meta-dimethyl-decorated counterpart ZJNU-95.…”

“…The incorporated functionalities largely include the Lewis‐basic heteroatoms and polarized functional groups. For example, compared to their corresponding parent compounds, the isostructural analogues functionalized with NH 2 , [14] lactam, [15] and aminopyridine, [16] displayed significantly enhanced C 2 H 2 adsorption. Recently, we reported that relative to the pyridinic N atom, its N‐oxide moiety can substantially boost the C 2 H 2 uptake capacity [17] .…”