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Industrialization over the past two centuries has resulted in a continuous rise in global CO2emissions. These emissions are changing ecosystems and livelihoods. Therefore, methods are needed to capture these emissions from point sources and possibly from our atmosphere. Though the amount of CO2is rising, it is challenging to capture directly from air because its concentration in air is extremely low, 0.04%. In this study, amines installed inside metal–organic frameworks (MOFs) are investigated for the adsorption of CO2, including at low concentrations. The amines used are polyamidoamine dendrimers that contain many primary amines. Chemically reversible adsorption of CO2via carbamate formation was observed, as was enhanced uptake of carbon dioxide, likely via dendrimer-amide-based physisorption. Limiting factors in this initial study are comparatively low dendrimer loadings and slow kinetics for carbon dioxide uptake and release, even at 80 °C.

Transition metal sulfides show great promise for applications ranging from catalysis to electrocatalysis to photovoltaics due to their high stability and conductivity. Nickel sulfide, particularly known for its ability to electrochemically reduce protons to hydrogen gas nearly as efficiently as expensive noble metals, can be challenging to produce with certain surface site compositions or morphologies, e.g., conformal thin films. To this end, we employed atomic layer deposition (ALD), a preeminent method to fabricate uniform and conformal films, to construct thin films of nickel sulfide (NiSx) using bis(N,N′-di-tert-butylacetamidinato)nickel(II) (Ni(amd)2) vapor and hydrogen sulfide gas. Effects of experimental conditions such as pulse and purge times and temperature on the growth of NiSxwere investigated. These revealed a wide temperature range, 125–225 °C, over which self-limiting NiSxgrowth can be observed. In situquartz crystal microbalance (QCM) studies revealed conventional linear growth behavior for NiSxfilms, with a growth rate of 9.3 ng/cm2per cycle being obtained. The ALD-synthesized films were characterized using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) methods. To assess the electrocatalyitic activity of NiSxfor evolution of molecular hydrogen, films were grown on conductive-glass supports. Overpotentials at a current density of 10 mA/cm2were recorded in both acidic and pH 7 phosphate buffer aqueous reaction media and found to be 440 and 576 mV, respectively, with very low NiSxloading. These results hint at the promise of ALD-grown NiSxmaterials as water-compatible electrocatalysts.

Developing structurally well-defined, supported oxide catalysts remains a significant challenge. Here, we report the grafting of Nb(V) oxide sites onto the nodes of the Zr-based metal organic framework (MOF) NU-1000as a stable, well-defined catalyst support. Nb(V) oxide was deposited with loadings up to 1.6 mmol/g via two postsynthetic methods: atomic layer deposition in a MOF, and solution-phase grafting in a MOF. Difference envelope density measurements indicated that the two synthetic methods resulted in different local structures of the Nb(V) ions within NU-1000. Despite their high Nb(V) loadings, which were equivalent to >60% surface coverage, nearly all Nb(V) sites of the MOF-supported catalysts were active sites for alkene epoxidation, as confirmed by phenylphosphonic acid titration. The MOF-supported catalysts were more selective than the control Nb-ZrO2catalyst for cyclohexene epoxidation with aqueous H2O2and were far more active on a gravimetric basis.

Composites of metal nanoparticles encapsulated in metal–organic frameworks (NP@MOFs) have emerged as heterogeneous catalysts for regioselective reactions. While numerous NP@MOF composite combinations have been synthesized, characterization of the nanoparticle–MOF interface and the encapsulated nanoparticle surface have yet to be determined. In this work, Pt@ZIF-8 synthesized by the controlled encapsulation method was chosen as a representative NP@MOF, and in situ characterization methods coupled with density functional theory (DFT) calculations were used to probe the nanoparticle surface. CO adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed that Pt@ZIF-8 exhibits red-shifted linear- and bridge-bound CO peaks and a linear peak associated with cationic Pt. DFT calculations and 1H NMR suggest that these sites arise from the binding and electronic donation of the MOF linker, 2-methylimidazole, to the Pt surface. DRIFTS under argon reveals that linker fragments may be present on the Pt nanoparticle surface, suggesting a reaction between the nanoparticle and the MOF linker during controlled encapsulation synthesis. Finally, CO oxidation reveals via DRIFTS that the red-shifted linear CO and bridging CO sites are active sites, while the cationic Pt is not. Overall, these results show that Pt@ZIF-8 contains unique Pt surface sites and indicate that the nanoparticle–MOF interface contains a heterogeneous mixture of framework 2-methylimidazole, free-standing 2-methylimidazole, and linker fragments. These findings expose the complex nature of the nanoparticle surface in NP@MOF composites and demonstrate the importance of characterizing their surface to understand their catalytic behavior.

Solvent-assisted linker exchange (SALE) has recently emerged as an attractive strategy for the synthesis of metal–organic frameworks (MOFs) that are unobtainable via traditional synthetic pathways. Herein we present the first example of selective SALE in which only the benzimiadazolate-containing linkers in a series of mixed-linker zeolitic imidazolate frameworks (ZIF-69, -78, and -76) are replaced. The resultant materials (SALEM-10, SALEM-10b, and SALEM-11, respectively) are isostructural to the parent framework and in each case contain trifluoromethyl moieties. We therefore evaluated each of these materials for their hydrophobicity in condensed and gas phases. We expect that selective SALE will significantly facilitate the design of improved, and potentially complex, MOF materials with new and unusual properties.

We report direct measurements of the excess polarizability volumes of butadiyne-bridged zinc porphyrin dimers at singly β-to-β (1Zn) and doubly β-to-β (2Zn) positions using the transient dc photoconductivity (TDCP) technique. The excess polarizability volumes of the singlet exciton for 1Znand 2Znare 110 and 270 Å3, respectively, while those of the triplet exciton are ∼100 Å3for both dimers. Our measurements suggest that the singlet exciton is mainly localized on one porphyrin subunit for 1Zn, similar to the case for the porphyrin monomer. While the exciton is fully delocalized on two porphyrin subunits in the case of meso-to-meso linked dimer (3Zn), the extent of exciton localization/delocalization for doubly β-to-β linked dimer lies between those of singly β-to-β and meso-to-meso linked dimers. Electronic structure calculations show that the dramatically different extents of exciton localization/delocalization are the results of frontier orbital coefficients being small at β positions but large at meso positions. Two butadiyne linkages between the porphyrins at β positions (2Zn) clearly facilitate electronic communication between the two porphyrin subunits by virtue of stabilization of cumulenic charge resonance structures through enforced planarity.

A new pillar-MOF [Zn2(L)(DABCO)] was solvothermally synthesized by using a new linker (L = 4,4′-(1,4-phenylenebis(3,5-dimethyl-1H-pyrazole-4,1-diyl))dibenzoic acid), Zn(NO3)2·6H2O, and triethylenediamine (DABCO) as pillar linker. It was characterized using single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) and tested for CO2adsorption. It exhibits dinuclear paddle–wheel nodes where the Zn(II) cations are coordinated by four equatorial L linkers generating two-dimensional sheets. DABCO acted as a pillar binding the sheets to obtain a neutral three-dimensional framework that shows one-dimensional square channels. The new pillar-layered MOF presents micro- and mesopores, and its crystallinity is preserved after activation at 160 °C × 16 h and adsorption of CO2. Due to the presence of the pyrazole nitrogen atoms in the framework, which have an increased affinity toward CO2, this new material exhibited a reasonable CO2uptake capacity and a low isosteric enthalpy of adsorption (Hads).