Kinetic Probes of the Origin of Activity in MOF-Based C–H Oxidation Catalysts

The development of homogeneous catalysis is enabled by the availability of a rich toolkit of kinetics experiments, such as the Hg-drop test, that differentiate catalytic activity at ligand-supported metal complexes from potential heterogeneous catalysts derived from decomposition of molecular species. Metal-organic frameworks (MOFs) have garnered significant attention as platforms for catalysis at site-isolated, interstitial catalyst sights. Unlike homogeneous catalysis, relatively few strategies have been advanced to evaluate the origin of catalytic activity in MOF-promoted reactions. Many of the MOFs that have been examined as potential catalysts are comprised of molecular constituents that represent viable catalysts in the absence of the extended MOF lattice, and thus interfacial sites and leached homogeneous species represent potential sources of catalyst activity. Here, we demonstrate that analysis of deuterium kinetic isotope effects (KIEs) and olefin epoxidation diastereoselectivity provides direct probes of the origin of catalytic activity in MOF-promoted oxidation reactions. These analyses support direct involvement of lattice-based Fe sites in the turnover-limiting step of C–H activation with Fe-MOF-74-based materials (i.e., the MOF functions as a bona fide catalyst) and evidence that Cu2-based MOF MIL-125-Cu2O2 functions as a solid-state initiator for solution-phase oxidation chemistry and is not involved in the turnover limiting step (i.e., the MOF does not function as a catalyst). We anticipate that the simple experiments described here will provide a valuable tool for clarifying the role of MOFs in C–H oxidation reactions.

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

In homogeneous catalysis solvent is an inherent part of the catalytic system. As such, it must be considered in the computational modeling. The most common approach to include solvent effects in quantum mechanical calculations is by means of continuum solvent models. When they are properly used, average solvent effects are efficiently captured, mainly those related with solvent polarity. However, neglecting atomistic description of solvent molecules has its limitations, and continuum solvent models all alone cannot be applied to whatever situation. In many cases, inclusion of explicit solvent molecules in the quantum mechanical description of the system is mandatory. The purpose of this article is to highlight through selected examples what are the reasons that urge to go beyond the continuum models to the employment of micro-solvated (cluster-continuum) of fully explicit solvent models, in this way setting the limits of continuum solvent models in computational homogeneous catalysis. These examples showcase that inclusion of solvent molecules in the calculation not only can improve the description of already known mechanisms but can yield new mechanistic views of a reaction. With the aim of systematizing the use of explicit solvent models, after discussing the success and limitations of continuum solvent models, issues related with solvent coordination and solvent dynamics, solvent effects in reactions involving small, charged species, as well as reactions in protic solvents and the role of solvent as reagent itself are successively considered.

Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

The development of efficient biomass valorization is imperative for the future sustainable production of chemicals and fuels. Particularly, the last decade has witnessed the development of a plethora of effective and selective transformations of bio-based furanics using homogeneous organometallic catalysis under mild conditions. In this review, we describe some of the advances regarding the conversion of target furanics into value chemicals, monomers for high-performance polymers and materials, and pharmaceutical key intermediates using homogeneous catalysis. Finally, the incorporation of furanic skeletons into complex chemical architectures by multifunctionalization routes is also described.

On the Importance of Considering Multinuclear Metal Sites in Homogeneous Catalysis Modeling

In this short review, we provide an account of a number of computational studies of catalytic reaction mechanisms carried out in our groups. We focus in particular on studies in which we came to realize during the course of the investigation that the active catalytic species was a bimetallic complex, rather a monometallic one as previously assumed. In some cases, this realization was in part prompted by experimental observations, but careful exploration based on computation of the speciation of the metal precursor also provided a powerful guide: it is often possible to predict that bimetallic species (intermediates or transition states) lie lower in free energy than a priori competitive monometallic species. In this sense, we argue that in organometallic catalysis, the rule whereby “two is better than one” turns out to be relevant much more often than one might expect.

Conversion of organosolv pretreated hardwood biomass into 5-hydroxymethylfurfural (HMF) by combining enzymatic hydrolysis and isomerization with homogeneous catalysis

Background Over the last few years, valorization of lignocellulosic biomass has been expanded beyond the production of second-generation biofuels to the synthesis of numerous platform chemicals to be used instead of their fossil-based counterparts. One such well-researched example is 5-hydroxymethylfurfural (HMF), which is preferably produced by the dehydration of fructose. Fructose is obtained by the isomerization of glucose, which in turn is derived by the hydrolysis of cellulose. However, to avoid harsh reaction conditions with high environmental impact, an isomerization step towards fructose is necessary, as fructose can be directly dehydrated to HMF under mild conditions. This work presents an optimized process to produce fructose from beechwood biomass hydrolysate and subsequently convert it to HMF by employing homogeneous catalysis. Results The optimal saccharification conditions were identified at 10% wt. solids loading and 15 mg enzyme/gsolids, as determined from preliminary trials on pure cellulose (Avicel® PH-101). Furthermore, since high rate glucose isomerization to fructose requires the addition of sodium tetraborate, the optimum borate to glucose molar ratio was determined to 0.28 and was used in all experiments. Among 20 beechwood solid pulps obtained from different organosolv pretreatment conditions tested, the highest fructose production was obtained with acetone (160 °C, 120 min), reaching 56.8 g/100 g pretreated biomass. A scale-up hydrolysis in high solids (25% wt.) was then conducted. The hydrolysate was subjected to isomerization eventually leading to a high-fructose solution (104.5 g/L). Dehydration of fructose to HMF was tested with 5 different catalysts (HCl, H3PO4, formic acid, maleic acid and H-mordenite). Formic acid was found to be the best one displaying 79.9% sugars conversion with an HMF yield and selectivity of 44.6% and 55.8%, respectively. Conclusions Overall, this work shows the feasibility of coupling bio- and chemo-catalytic processes to produce HMF from lignocellulose in an environmentally friendly manner. Further work for the deployment of biocatalysts for the oxidation of HMF to its derivatives could pave the way for the emergence of an integrated process to effectively produce biobased monomers from lignocellulose.