A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C₂ Hydrocarbons and CO₂

Abstract

Introduction of pore partition agents into hexagonal channels of MIL‐88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4,4′‐dipyridylsulfide (dps) ligands. One third of open metal sites in the acs net are retained in pacs MOFs; two thirds are used for pore‐space partition. The Co2V‐pacs MOFs exhibit near or at record high uptake capacities for C2H2, C2H4, C2H6, and CO2 among MOFs. The storage capacity of C2H2 is 234 cm3 g−1 (298 K) and 330 cm3 g−1 (273 K) at 1 atm for CPM‐733‐dps (the Co2V‐BDC form, BDC=1,4‐benzenedicarboxylate). These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low‐energy‐cost adsorbent regeneration. CPM‐733‐dps is stable and shows no loss of C2H2 adsorption capacity following multiple adsorption–desorption cycles.

Theoretical investigation of C1–C4 hydrocarbons adsorption and separation in a porous metallocavitand

“…The C 2 H 2 adsorption in PPX is 2.80 mmol g −1 , although the adsorption is not very good but performs better than UPC-98, 50 UMCM-151, 51 PFC-5, 52 FIR-125, 53 NUM-9a, 54 JLU-Liu45, 55 Zr-OBBA, 55 PFC-1/-2, 56 NUM-7, 57 Cu–F-pymo, 58 MOF 1/MOF 2, 59 UPC-99, 60 NbU-1. 61 C 2 H 4 adsorption was also impressive with 4.26 mmol g −1 and only MFM-300(In) 62 (4.9 mmol g −1 ), and Dps-VCo-BDC (7.41 mmol g −1 )/tpt-VCo-BDC(6.29 mmol g −1 ) 63 MOF is higher than PPX limit. Similarly, the adsorption of C 2 H 6 in PPX is quite higher with 4.22 mmol g −1 which is better than many of the notable MOFs and only Mg-MOF74(6.1 mmol g −1 ) 47 and its functionalized MOF tpt-Mg-MOF-74 (5.4 mmol g −1 ), MFM-300(In) (5.1 mmol g −1 ), 62 Gly@HKUST-1s (6.47 mmol g −1 ), 64 Dps-VCo-BDC (8.03 mmol g −1 )/tpt-VCo-BDC (6.69 mmol g −1 ), 63 and NPU-1 (4.50 mmol g −1 )/NPU-2(4.44 mmol g −1 ) 65 are higher than the PPX.…”

“…61 C 2 H 4 adsorption was also impressive with 4.26 mmol g −1 and only MFM-300(In) 62 (4.9 mmol g −1 ), and Dps-VCo-BDC (7.41 mmol g −1 )/tpt-VCo-BDC(6.29 mmol g −1 ) 63 MOF is higher than PPX limit. Similarly, the adsorption of C 2 H 6 in PPX is quite higher with 4.22 mmol g −1 which is better than many of the notable MOFs and only Mg-MOF74(6.1 mmol g −1 ) 47 and its functionalized MOF tpt-Mg-MOF-74 (5.4 mmol g −1 ), MFM-300(In) (5.1 mmol g −1 ), 62 Gly@HKUST-1s (6.47 mmol g −1 ), 64 Dps-VCo-BDC (8.03 mmol g −1 )/tpt-VCo-BDC (6.69 mmol g −1 ), 63 and NPU-1 (4.50 mmol g −1 )/NPU-2(4.44 mmol g −1 ) 65 are higher than the PPX. One should also notice the binding energy and selectivity, the binding energy is higher than many of the reported systems, and the selectivity of C2 HCs distinct and have the potential to separate each component.…”

A {Ni12}‐Wheel‐Based Metal–Organic Framework for Coordinative Binding of Sulphur Dioxide and Nitrogen Dioxide

“…Metal‐organic frameworks (MOFs) have emerged as multifunctional materials owing to their high internal surface area and capability of precise edition of pore functionality [1–3] . The fine tuning of pore size and geometry, framework topology, and chemical functionality has resulted in targeted applications, including gas adsorption, separation, catalysis, substrate binding and delivery, where host‐guest interactions present and often dominate the materials function [4–13] . Thus, deriving deep understanding and placing control on the mechanism of host‐guest interactions are of critical importance for the design and discovery of new functional MOF materials.…”

Photochemical In Situ Exfoliation of Metal–Organic Frameworks for Enhanced Visible‐Light‐Driven CO2 Reduction

“…The CO 2 uptake values of 2D-Ni 2 TCPE and 2D-Co 2 TCPE at 273 K were determined to be 36.5 and 41.7 cm 3 g À1 , respectively, suggesting their potential for CO 2 adsorption ( Figure S4). [17] The UV/Vis absorption spectra of these 2D MOFs reveals a broad absorption in the region of 450-800 nm, which indicates their potential for photocatalytic reactions (Figure S5). According to the Tauc plot, band gap energies (E g ) of 2.63 and 2.70 eV were obtained for 2D-Ni 2 TCPE and 2D-Co 2 TCPE, respectively ( Figure S6).…”