Computational Mechanism of Methyl Levulinate Conversion to γ-Valerolactone on UiO-66 Metal Organic Frameworks.

Metal-organic frameworks (MOFs) are gaining importance in the field of biomass conversion and valorization due to their porosity, well-defined active sites, and broad tunability. But for a proper catalyst design, we first need detailed insight of the system at the atomic level. Herein, we present the reaction mechanism of methyl levulinate to γ-valerolactone on Zr-based UiO-66 by means of periodic density functional theory (DFT). We demonstrate the role of Zr-based nodes in the catalytic transfer hydrogenation (CTH) and cyclization steps. From there, we perform a computational screening to reveal key catalyst modifications to improve the process, such as node doping and linker exchange.

Enhanced Performance of Zirconium-Doped Ceria Catalysts for the Methoxycarbonylation of Anilines.

The methoxycarbonylation of anilines stands as an attractive method for the phosgene-free production of carbamates. Despite the high yields obtained for ceria catalysts, the reduction of the amount of side products and the prevention of catalyst deactivation still represent major hurdles in this chemistry. One advantage of ceria is the possibility of tuning its reactivity by doping its lattice with other metals. In the present work, a series of doped ceria-based materials, prepared by substitution with metals, are evaluated in the methoxycarbonylation of 2,4-diaminotoluene with dimethyl carbonate. Among all catalysts, containing Eu, Hf, La, Pr, Sm, Tb, Y or Zr, ceria promoted with 2 mol % Zr exhibited 96 % selectivity towards the desired carbamates, improving the pure CeO2 catalyst. Density functional theory demonstrates that two descriptors are needed: 1) a geometric factor that governs the reduction of energy barriers for carbamate formation through ureas; 2) catalyst basicity as N-H bonds need to be activated. Assessment in subsequent reaction cycles revealed that the CeO2 -ZrO2 catalyst is more stable than bulk CeO2 , along with the reduction of fouling processes.

Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides.

The physical and chemical properties of oxides are defined by the presence of oxygen vacancies. Experimentally, non-defective structures are almost impossible to achieve due to synthetic constraints. Therefore, it is crucial to account for vacancies when evaluating the characteristics of these materials. The electronic structure of oxygen-depleted oxides deeply differs from that of the native forms, in particular, of reducible metal oxides, where excess electrons can localize in various distinct positions. In this perspective, we present recent developments from our group describing the complexity of these defective materials that highlight the need for an accurate description of (i) intrinsic vacancies in polar terminations, (ii) multiple geometries and complex electronic structures with several states attainable at typical working conditions, and (iii) the associated dynamics for both vacancy diffusion and the coexistence of more than one electronic structure. All these aspects widen our current understanding of defects in oxides and need to be adequately introduced in emerging high-throughput screening methodologies.

One Oxygen Vacancy, Two Charge States: Characterization of Reduced α-MoO3(010) through Theoretical Methods.

Molybdenum oxides are finding increasing applications that rely on their redox character. For the most common polymorph, α-MoO3, oxygen vacancy formation leaves two electrons on the surface that can be stored as small polarons. Detailed density functional theory calculations that properly account for the self-interaction term, Ueff = 3.5 eV, show that the vacancy generates two different configurations: either two Mo5+ centers (Mo5+□ and Mo5+═O) or a single double-reduced Mo4+. These states are separated by 0.22 eV with a barrier for interconversion of 0.33 eV, and thus both are populated at catalytic temperatures, as shown by first-principles molecular dynamics. At higher reduction levels, vacancies can only be accumulated along a preferential direction and the energy difference between the 2×Mo5+ and Mo4+ configurations is reduced. These results point out the need for a revision of the experimental assignments based on our characterization that includes charges, vibrational frequencies, and XPS signatures.

Shape control in concave metal nanoparticles by etching.

The shape control of nanoparticles constitutes one of the main challenges in today's nanotechnology. The synthetic procedures are based on trial-and-error methods and are difficult to rationalize as many ingredients are typically used. For instance, concave nanoparticles exhibiting high-index facets can be obtained from Pt with different HCl treatments. These structures present exceptional capacities when are employed as catalysts in electrochemical processes, as they maximize the activity per mass unit of the expensive material. Here we show how atomistic simulations based on density functional theory that take into account the environment can predict the morphology for the nanostructures and how it is even possible to address the appearance of concave structures. To describe the control by etching, we have reformulated the Wulff construction through the use of a geometric model that leads to concave polyhedra, which have a larger surface-to-volume ratio compared to that for nanocubes. Such an increase makes these sorts of nanoparticles excellent candidates to improve electrocatalytic performance.

The Active Molybdenum Oxide Phase in the Methanol Oxidation to Formaldehyde (Formox Process): A DFT Study.

Methanol is oxidised to formaldehyde by the Formox process, in which molybdenum oxides, usually doped with iron, are the catalyst. The active phase of the catalysts and the reasons for the selectivity observed are still unknown. We present a density functional theory based study that indicates the unique character of Mo(VI)¢Mo(IV) pairs as the most active and selective sites and indicates the active sites on the surface, the controlling factors of selectivity, and the role of the dopant. Iron reduces the energy requirements of the redox Mo(VI)¢Mo(IV) pair by acting as an electron reservoir that sets in if required. Our present study paves the way towards a better understanding of the process.

DFT and MP2 study of the interaction between corannulene and alkali cations.

Corannulene is an unsaturated hydrocarbon composed of fused rings, with one central five-membered ring and five peripheral six-membered rings. Its structure can be considered as a portion of C60. Corannulene is a curved π surface, but unlike C60, it has two accessible different faces: one concave (inside) and one convex (outside). In this work, computational modeling of the binding between alkali metal cations (Li(+), Na(+), and K(+)) and corannulene has been performed at the DFT and MP2 levels. Different corannulene···M(+) complexes have been studied and the transition states interconnecting local minima were located. The alkali cations can be bound to a five or six membered ring in both faces. At the DFT level, binding to the convex face (outside) is favored relative to the concave face for the three alkali cations studied, as it was previously published. This out preference was found to decrease as cation size increases. At the MP2 level, although a similar trend is found, some different conclusions related to the in/out preference were obtained. According to our results, migration of cations can take place on the convex or on the concave face. Also, there are two ways to transform a concave complex in a convex complex: migration across the edge of corannulene and bowl-to-bowl inversion.