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CALF-20, a Zn-triazolate-based metal-organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption of water severely limits its performance when the relative humidity (RH) exceeds 40%, limiting the potential implementation of CALF-20 in practical settings where CO2 is saturated with moisture, such as post-combustion flue gas. In this work, three newly designed MOFs related to CALF-20, denoted as NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyl-triazolate linkers are presented. Inclusion of methyl groups in the linker is proposed as a strategy to improve CO2 uptake in the presence of water. Notably, both CALF-20M-w and CALF-20M-e retain over 20% of their initial CO2 capture efficiency at 70% RH – a threshold at which CALF-20 shows negligible CO2 uptake. Grand canonical Monte Carlo (GCMC) simulations reveal that the methyl group hinders water network formation in the pores of CALF-20M-w and CALF-20M-e and enhances their CO2 selectivity over N2 in the presence of high moisture content. Moreover, calculated radial distribution functions indicate that introducing the methyl group into the triazolate linker increases the distance between water molecules and Zn coordination bonds, offering insights into the origin of the enhanced moisture stability observed for CALF-20M-w and CALF-20M-e relative to CALF-20. Overall, this straightforward design strategy has afforded more robust sorbents that can potentially meet the challenge of effectively capturing CO2 in practical industrial applications. 

The speciation and structure of Cu ions and complexes in chabazite (SSZ-13) zeolites, which are relevant catalysts for nitrogen oxide reduction and partial methane oxidation, depend on material composition and reaction environment. Ultraviolet-visible (UV-Vis) spectra of Cu-SSZ-13 zeolites synthesized to contain specific Cu site motifs, together with ab initio molecular dynamics and time-dependent density functional theory calculations, were used to test the ability to relate specific spectroscopic signatures to specific site motifs. Geometrically distinct arrangements of two framework Al atoms in six-membered rings are found to exchange Cu 2+ ions that become spectroscopically indistinguishable after accounting for the finite-temperature fluctuations of the Cu coordination environment. Nominally homogeneous single Al exchange sites are found to exchange a heterogeneous mixture of [CuOH] + monomers, O- and OH-bridged Cu dimers, and larger polynuclear complexes. The UV-Vis spectra of the latter are sensitive to framework Al proximity, to precise ligand environment, and to finite-temperature structural fluctuations, precluding the precise assignment of spectroscopic features to specific Cu structures. In all Cu-SSZ-13 samples, these dimers and larger complexes are reduced by CO to Cu + sites at 523 K, leaving behind isolated [CuOH] + sites with a characteristic spectroscopic identity. The various mononuclear and polynuclear Cu 2+ species are distinguishable by their different responses to reducing environments, with implications for their relevance to catalytic redox reactions.