Pyrazine‐linked hybrid ultramicroporous (pore size <7 Å) materials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO2 over small gas molecules, including light hydrocarbons. That the prototypal pyrazine‐linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX‐3‐Zn, mainly through substitution of the metal and/or the inorganic pillar. Herein, we report that two isostructural aminopyrazine‐linked HUMs, MFSIX‐17‐Ni (17=aminopyrazine; M=Si, Ti), which we had anticipated would offer even stronger affinity for CO2 than their pyrazine analogs, unexpectedly exhibit reduced CO2 affinity but enhanced C2H2 affinity. MFSIX‐17‐Ni are consequently the first physisorbents that enable single‐step production of polymer‐grade ethylene (>99.95 % for SIFSIX‐17‐Ni) from a ternary equimolar mixture of ethylene, acetylene and CO2 thanks to coadsorption of the latter two gases. We attribute this performance to the very different binding sites in MFSIX‐17‐Ni versus SIFSIX‐3‐Zn.
The trade-off between selectivity and adsorption capacity with porous materials is a major roadblock to reducing the energy footprint of gas separation technologies. To address this matter, we report herein a systematic crystal engineering study of C 2 H 2 removal from CO 2 in a family of hybrid ultramicroporous materials (HUMs). The HUMs are composed of the same organic linker ligand, 4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, pypz, three inorganic pillar ligands, and two metal cations, thereby affording six isostructural pcu topology HUMs. All six HUMs exhibited strong binding sites for C 2 H 2 and weaker affinity for CO 2 . The tuning of pore size and chemistry enabled by crystal engineering resulted in benchmark C 2 H 2 /CO 2 separation performance. Fixed-bed dynamic column breakthrough experiments for an equimolar (v/v = 1:1) C 2 H 2 /CO 2 binary gas mixture revealed that one sorbent, SIFSIX-21-Ni, was the first C 2 H 2 selective sorbent that combines exceptional separation selectivity (27.7) with high adsorption capacity (4 mmol$g À1 ).
The potential implementation of extreme ultraviolet (EUV) lithography into next generation device processing is bringing urgency to identify resist materials that optimize EUV lithographic performance. Inorganic/organic hybrid nanoparticles or clusters constitute a promising new class of materials, with high EUV sensitivity from the core and tunable chemistry through the coordinating ligands. Development of a thorough mechanistic understanding of the solubility switching reactions in these materials is an essential first step toward their implementation in patterning applications but remains challenging due to the complexity of their structures, limitations in EUV sources, and lack of rigorous in situ characterization. Here we report a mechanistic investigation of the solubility switching reactions in hybrid clusters comprised of a small HfOx core capped with a methacrylic acid ligand shell (HfMAA). We show that EUV-induced reactions can be studied by performing in situ IR spectroscopy of electronirradiated films using a variable energy electron gun. Combining additional ex situ metrology, we track the chemical evolution of the material at each stage of a typical resist processing sequence. For instance, we find that a crosslinking reaction initiated by decarboxylation of the methacrylate ligands under electron irradiation constitutes the main solubility switching mechanism, although there are also chemical changes imparted by a typical the post application bake (PAB) step alone. Lastly, synchrotronbased IR microspectroscopy measurements of EUV-irradiated HfMAA films enable a comparison of reactions induced by EUV vs electron beam irradiation of the same resist material, yielding important insight into the use of electron beam irradiation as an experimental model for EUV exposure.
Engineering the structural flexibility of MOF materials for separation-related applications remains a great challenge. We present here a strategy of mixing rigid and soft linkers in a MOF structure to achieve tunable structural flexibility, as exemplified in a series of stable isostructural Zr-MOFs built with natural C4 linkers (fumaric acid, succinic acid and malic acid). As shown by the differences in linker bond stretching and rotational freedom, these MOFs display distinct responsive dynamics to external stimuli, namely temperature or guest adsorption. Comprehensive in-situ characterizations reveal a clear correlation between linker character and MOF dynamic behavior, which leads to the discovery of a multivariate flexible MOF. It shows an optimal combination of both good CO 2 working capacity and significantly enhanced CO 2 /N 2 selectivity. In principle, it provides a new avenue for potentially improving the ability of microporous MOFs to separate other gaseous and liquid mixtures. chemical mixtures, including liquid and gaseous phases. Therefore, it serves as a suitable example that engineering the structural flexibility of MOF materials could constitute a promising and versatile strategy for improving MOF separation performance, or even realizing new applications.
Adsorptive separation by porous solids provides an energy-efficient alternative for the purification of important chemical species compared to energy-intensive distillations. Particularly, the separation of linear hexane isomers from its branched counterparts is crucial to produce premium grade gasoline with high research octane number (RON). Herein, we report the synthesis of a new, flexible zinc-based metal–organic framework, [Zn5(μ3-OH)2(adtb)2(H2O)5·5 DMA] (Zn-adtb), constructed from a butterfly shaped carboxylate linker with underlying (4,8)-connected scu topology capable of separating the C6 isomers nHEX, 3MP, and 23DMB. The sorbate–sorbent interactions and separation mechanisms were investigated and analyzed through in situ FTIR, solid state NMR measurements and computational modeling. These studies reveal that Zn-adtb discriminates the nHEX/3MP isomer pair through a kinetic separation mechanism and the nHEX/23DMB isomer pair through a molecular sieving mechanism. Column breakthrough measurements further demonstrate the efficient separation of linear nHEX from the mono- and dibranched isomers.
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