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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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Low-cost Ni(OH)2-based nanomaterials with various structures and morphologies are promising catalysts for efficient oxygen evolution reactions (OERs). However, homogenous Ni(OH)2 nanomaterials with abundant active sites suffer from low conductivity and easy aggregation, resulting in low catalytic activity and stability. Here, we report a new synthetic method capable of generating abundant and confined S-doped β-Ni(OH)2 nanoparticles (NPs) (3–5 nm) within a 3D semiconductor substrate, metal-chalcogenide semiconductor zeolite (CSZ). This method operates via sequential fluoride-assisted cationic stripping and in situ Ni(OH)2 generation and is demonstrated here as an effective method to synthesize Ni2+-containing CSZ that are known to defy direct synthesis. The resulting composite (denoted Ni(OH)2 NPs@CSZ) exhibited excellent OER performance with a very low overpotential of only 212 mV at a current density of 10 mA cm−2 in O2-saturated 1 M KOH solution, and low Tafel slope of 64.2 mV dec−1, which is superior to that of benchmark IrO2. DFT calculations indicate that the interaction between the embedded Ni(OH)2 NPs and the dopant, S2−, from the host CSZ played a crucial role in improving OER performance. This work provides a new path for developing high-performance Ni(OH)2-based OER catalysts and may also serve as a general approach for loading large amounts of other catalytically active NPs into semiconducting open frameworks to further optimize electrocatalytic performance. [ABSTRACT FROM AUTHOR]