A Critical Assessment on Calculating Vibrational Spectra in Nanostructured Materials.

Vibrational spectroscopy is an omnipresent spectroscopic technique to characterize functional nanostructured materials such as zeolites, metal-organic frameworks (MOFs), and metal-halide perovskites (MHPs). The resulting experimental spectra are usually complex, with both low-frequency framework modes and high-frequency functional group vibrations. Therefore, theoretically calculated spectra are often an essential element to elucidate the vibrational fingerprint. In principle, there are two possible approaches to calculate vibrational spectra: (i) a static approach that approximates the potential energy surface (PES) as a set of independent harmonic oscillators and (ii) a dynamic approach that explicitly samples the PES around equilibrium by integrating Newton's equations of motions. The dynamic approach considers anharmonic and temperature effects and provides a more genuine representation of materials at true operating conditions; however, such simulations come at a substantially increased computational cost. This is certainly true when forces and energy evaluations are performed at the quantum mechanical level. Molecular dynamics (MD) techniques have become more established within the field of computational chemistry. Yet, for the prediction of infrared (IR) and Raman spectra of nanostructured materials, their usage has been less explored and remain restricted to some isolated successes. Therefore, it is currently not a priori clear which methodology should be used to accurately predict vibrational spectra for a given system. A comprehensive comparative study between various theoretical methods and experimental spectra for a broad set of nanostructured materials is so far lacking. To fill this gap, we herein present a concise overview on which methodology is suited to accurately predict vibrational spectra for a broad range of nanostructured materials and formulate a series of theoretical guidelines to this purpose. To this end, four different case studies are considered, each treating a particular material aspect, namely breathing in flexible MOFs, characterization of defects in the rigid MOF UiO-66, anharmonic vibrations in the metal-halide perovskite CsPbBr3, and guest adsorption on the pores of the zeolite H-SSZ-13. For all four materials, in their guest- and defect-free state and at sufficiently low temperatures, both the static and dynamic approach yield qualitatively similar spectra in agreement with experimental results. When the temperature is increased, the harmonic approximation starts to fail for CsPbBr3 due to the presence of anharmonic phonon modes. Also, the spectroscopic fingerprints of defects and guest species are insufficiently well predicted by a simple harmonic model. Both phenomena flatten the potential energy surface (PES), which facilitates the transitions between metastable states, necessitating dynamic sampling. On the basis of the four case studies treated in this Review, we can propose the following theoretical guidelines to simulate accurate vibrational spectra of functional solid-state materials: (i) For nanostructured crystalline framework materials at low temperature, insights into the lattice dynamics can be obtained using a static approach relying on a few points on the PES and an independent set of harmonic oscillators. (ii) When the material is evaluated at higher temperatures or when additional complexity enters the system, e.g., strong anharmonicity, defects, or guest species, the harmonic regime breaks down and dynamic sampling is required for a correct prediction of the phonon spectrum. These guidelines and their illustrations for prototype material classes can help experimental and theoretical researchers to enhance the knowledge obtained from a lattice dynamics study.

How Water and Ion Mobility Affect the NMR Fingerprints of the Hydrated JBW Zeolite: A Combined Computational-Experimental Investigation.

An important aspect within zeolite synthesis is to make fully tunable framework materials with controlled aluminium distribution. A major challenge in characterising these zeolites at operating conditions is the presence of water. In this work, we investigate the effect of hydration on the 27 Al NMR parameters of the ultracrystalline K,Na-compensated aluminosilicate JBW zeolite using experimental and computational techniques. The JBW framework, with Si/Al ratio of 1, is an ideal benchmark system as a stepping stone towards more complicated zeolites. The presence and mobility of water and extraframework species directly affect NMR fingerprints. Excellent agreement between theoretical and experimental spectra is obtained provided dynamic methods are employed with hydrated structural models. This work shows how NMR is instrumental in characterising aluminium distributions in zeolites at operating conditions.

Atomistic insight in the flexibility and heat transport properties of the stimuli-responsive metal-organic framework MIL-53(Al) for water-adsorption applications using molecular simulations.

To exploit the full potential of metal-organic frameworks as solid adsorbents in water-adsorption applications, many challenges remain to be solved. A more fundamental insight into the properties of the host material and the influence that water exerts on them can be obtained by performing molecular simulations. In this work, the prototypical flexible MIL-53(Al) framework is modelled using advanced molecular dynamics simulations. For different water loadings, the presence of water is shown to affect the relative stability of MIL-53(Al), triggering a phase transition from the narrow-pore to the large-pore phase at the highest considered loading. Furthermore, the effect of confinement on the structural organisation of the water molecules is also examined for different pore volumes of MIL-53(Al). For the framework itself, we focus on the thermal conductivity, as this property plays a decisive role in the efficiency of adsorption-based technologies, due to the energy-intensive adsorption and desorption cycles. To this end, the heat transfer characteristics of both phases of MIL-53(Al) are studied, demonstrating a strong directional dependence for the thermal conductivity.

Theoretical and Spectroscopic Evidence of the Dynamic Nature of Copper Active Sites in Cu-CHA Catalysts under Selective Catalytic Reduction (NH3-SCR-NOx) Conditions.

The dynamic nature of the copper cations acting as active sites for selective catalytic reduction of nitrogen oxides with ammonia is investigated using a combined theoretical and spectroscopic approach. Ab initio molecular dynamics simulations of Cu-CHA catalysts in contact with reactants and intermediates at realistic operating conditions show that only ammonia is able to release Cu+ and Cu2+ cations from their positions coordinated to the zeolite framework, forming mobile Cu+(NH3)2 and Cu2+(NH3)4 complexes that migrate to the center of the cavity. Herein, we give evidence that such mobilization of copper cations modifies the vibrational fingerprint in the 800-1000 cm-1 region of the IR spectra. Bands associated with the lattice asymmetric T-O-T vibrations are perturbed by the presence of coordinated cations, and allow one to experimentally follow the dynamic reorganization of the active sites at operating conditions.

Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker.

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of α-pinene oxide. This reaction is particularly sensitive to the Brønsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Brønsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Brønsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.

A Supramolecular View on the Cooperative Role of Brønsted and Lewis Acid Sites in Zeolites for Methanol Conversion.

A systematic molecular level and spectroscopic investigation is presented to show the cooperative role of Brønsted acid and Lewis acid sites in zeolites for the conversion of methanol. Extra-framework alkaline-earth metal containing species and aluminum species decrease the number of Brønsted acid sites, as protonated metal clusters are formed. A combined experimental and theoretical effort shows that postsynthetically modified ZSM-5 zeolites, by incorporation of extra-framework alkaline-earth metals or by demetalation with dealuminating agents, contain both mononuclear [MOH]+ and double protonated binuclear metal clusters [M(µ-OH)2M]2+ (M = Mg, Ca, Sr, Ba, and HOAl). The metal in the extra-framework clusters has a Lewis acid character, which is confirmed experimentally and theoretically by IR spectra of adsorbed pyridine. The strength of the Lewis acid sites (Mg > Ca > Sr > Ba) was characterized by a blue shift of characteristic IR peaks, thus offering a tool to sample Lewis acidity experimentally. The incorporation of extra-framework Lewis acid sites has a substantial influence on the reactivity of propene and benzene methylations. Alkaline-earth Lewis acid sites yield increased benzene methylation barriers and destabilization of typical aromatic intermediates, whereas propene methylation routes are less affected. The effect on the catalytic function is especially induced by the double protonated binuclear species. Overall, the extra-framework metal clusters have a dual effect on the catalytic function. By reducing the number of Brønsted acid sites and suppressing typical catalytic reactions in which aromatics are involved, an optimal propene selectivity and increased lifetime for methanol conversion over zeolites is obtained. The combined experimental and theoretical approach gives a unique insight into the nature of the supramolecular zeolite catalyst for methanol conversion which can be meticulously tuned by subtle interplay of Brønsted and Lewis acid sites.

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach.

In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable determination of the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases, indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.