An Amino‐Functionalized Metal‐Organic Framework, Based on a Rare Ba₁₂(COO)₁₈(NO₃)₂ Cluster, for Efficient C₃/C₂/C₁ Separation and Preferential Catalytic Performance

Abstract

A barium(II) metal-organic framework (MOF) based on a predesigned amino-functionalized ligand, namely [Ba (L)(DMF)(H O)(NO ) ]⋅DMF⋅EtOH⋅2 H O (UPC-33) [H L=4,4'-((2-amino-5-carboxy-1,3-phenylene)bis(ethyne-2,1-diyl))dibenzoic acid] has been synthesized. UPC-33 is a 3-dimensional 3,18-connected network with fcu topology with a rare twelve-nuclear Ba (COO) (NO ) cluster. UPC-33 shows permanent porosity and a high adsorption heat of CO (49.92 kJ mol ), which can be used as a platform for selective adsorption of CO /CH (8.09). In addition, UPC-33 exhibits high separation selectivity for C light hydrocarbons with respect to CH (228.34, 151.40 for C H /CH , C H /CH at 273k and 1 bar), as shown by single component gas sorption and selectivity calculations. Due to the existence of -NH groups in the channels, UPC-33 can effectively catalyze Knoevenagel condensation reactions with high yield, and substrate size and electron dependency.

Flexible Microporous Framework Based on Pb4 Clusters for Highly Selective Storage and Separation of Energy Gases

“…When the temperature decreases to 273 K, the IAST predicted selectivities of C 2 H 2 /CH 4 , C 2 H 4 /CH 4 , C 2 H 6 /CH 4 , C 3 H 4 /CH 4 , C 3 H 6 /CH 4 , and C 3 H 8 /CH 4 (0.5:0.5) slightly increase to 17.65, 9.38, 13.32, 6317.94, 421.87, and 199.02, respectively (Figure c,d). It should be noted that the selectivities of FJI-H22-desolvated for C 2 H 6 /CH 4 at 298 K are similar to those of UTSA-35a and PCN-224, and are higher than the corresponding values of UPC-33, JLU-Liu51,and JLU-Liu37. ,, To our best knowledge, the selectivity of C 3 H 8 /CH 4 is higher than the corresponding values of UPC-33 , JLU-Liu5 , USTA-35a , and InOF-1. , …”

“…It should be noted that the selectivities of FJI-H22-desolvated for C 2 H 6 /CH 4 at 298 K are similar to those of UTSA-35a 31 and PCN-224, 32 and are higher than the corresponding values of UPC-33, JLU-Liu51,and JLU-Liu37. 14,33,34 To our best knowledge, the selectivity of C 3 H 8 /CH 4 is higher than the corresponding values of UPC-33, JLU-Liu5, USTA-35a, and InOF-1. 35,36 In addition, we also investigate the potential applications of FJI-H22 for CO 2 capture and separation.…”

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 .…”

A Stable Interpenetrated Zn-MOF with Efficient Light Hydrocarbon Adsorption/Separation Performance

“…The experimental results are summarized in Figure 3a , and CH 4 (5.9 cm 3 •g −1 , 0.26 mmol•g −1 ), respectively. It is noteworthy that UPC-98 has a higher adsorption capacity for C 3 H 8 than FJI-C4 (74.7 cm 3 • g −1 ), 26 1-mim (102.92 cm 3 •g −1 ), 1-eim (97.36 cm 3 •g −1 ), and 1pim (97.31 cm 3 •g −1 ), 27 lower than FJI-C1 (160.9 cm 3 •g −1 ) 28 at 273 K. At the same time, UPC-98 displays a higher sorption capacity for C 3 H 6 than UPC-33 (114.2 cm 3 •g −1 ), 29 but lower than UPC-102 (148.8 cm 3 •g −1 ), 30 illustrating that UPC-98 is an excellent material for storing C 3 H 6 and C 3 H 8 . The adsorption data compared to the reported MOFs are shown in Table S3.…”

“…As expected, UPC-98 displays a high sorption capacity for C 3 H 8 (118.4 cm 3 ·g –1 , 5.29 mmol·g –1 ), C 3 H 6 (120.5 cm 3 ·g –1 , 5.38 mmol·g –1 ), C 2 H 6 (29.5 cm 3 ·g –1 , 1.32 mmol·g –1 ), C 2 H 4 (31.3 cm 3 ·g –1 , 1.40 mmol·g –1 ), and C 2 H 2 (43.1 cm 3 ·g –1 , 1.92 mmol·g –1 ), but a relatively lower uptake of CH 4 (8.1 cm 3 ·g –1 , 0.36 mmol·g –1 ) at 273 K. After the temperature increased to 298 K, UPC-98 showed similar adsorption capacities to 273 K. The adsorption capacities are C 3 H 8 (97.4 cm 3 ·g –1 , 4.34 mmol·g –1 ), C 3 H 6 (116.5 cm 3 ·g –1 , 5.20 mmol·g –1 ), C 2 H 6 (45.4 cm 3 ·g –1 , 2.03 mmol·g –1 ), C 2 H 4 (17.6 cm 3 ·g –1 , 0.79 mmol·g –1 ), C 2 H 2 (30.2 cm 3 ·g –1 , 1.35 mmol·g –1 ), and CH 4 (5.9 cm 3 ·g –1 , 0.26 mmol·g –1 ), respectively. It is noteworthy that UPC-98 has a higher adsorption capacity for C 3 H 8 than FJI-C4 (74.7 cm 3 ·g –1 ), 1-mim (102.92 cm 3 ·g –1 ), 1-eim (97.36 cm 3 ·g –1 ), and 1-pim (97.31 cm 3 ·g –1 ), lower than FJI-C1 (160.9 cm 3 ·g –1 ) at 273 K. At the same time, UPC-98 displays a higher sorption capacity for C 3 H 6 than UPC-33 (114.2 cm 3 ·g –1 ), but lower than UPC-102 (148.8 cm 3 ·g –1 ), illustrating that UPC-98 is an excellent material for storing C 3 H 6 and C 3 H 8 . The adsorption data compared to the reported MOFs are shown in Table S3.…”