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Results for “host-guest catalysis”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Bioinspired Multicomponent Catalytic System for Converting Carbon Dioxide into Methanol Autocatalytically

Nature utilizes multicomponent catalyst systems to convert simple, abundant starting materials to complex molecules that are essential for life. In contrast, synthetic chemical transformations rarely adopt this strategy because the sophisticated supramolecular assemblies used by biology for active site separation and substrate trafficking are difficult to replicate. Herein, a method is described for multicomponent catalyst separation that involves encapsulating transition metal complexes in nanoporous materials called metal-organic frameworks. The multicomponent catalyst system was highly active for converting hydrogen and carbon dioxide to methanol, and it could be formulated so that it is readily recyclable. Moreover, an autocatalytic feature was uncovered that was only made possible by utilizing the multicomponent catalyst strategy employed. Furthermore, these results open avenues for obtaining fuel from abundant and renewable resources.

08 HYDROGEN↗
DOE OSTI2020

Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold

Abstract Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga 4 L 6 12− on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Heterogeneous Supramolecular Catalysis through Immobilization of Anionic M 4 L 6 Assemblies on Cationic Polymers

Although most of the currently developed supramolecular catalysts that emulate enzymatic reactivity with unique selectivity and activity through specific host-guest interactions work under homogeneous conditions, enzymes in nature can operate under heterogeneous conditions as membrane-bound enzymes. In order to develop such a heterogeneous system, an immobilized chiral supramolecular cluster Ga 4 1 6 ( 2 ) was introduced into cross-linked polymers with cationic functionalities. These heterogeneous supramolecular catalysts were used in aza-Prins and aza-Cope reactions and successfully applied to continuous-flow reactions. Additionally, they showed high durability and maintained high turnovers for long periods of time. In sharp contrast to the majority of examples of heterogenized homogeneous catalysts, the newly developed catalysts showed enhanced activity and robustness compared to those exhibited by the corresponding soluble cluster catalyst. An enantioenriched cluster was also immobilized to enable asymmetric catalysis, and activity and enantioselectivity of the supported chiral catalyst were maintained during recovery and reuse experiments and under a continuous-flow process. Significantly, the structure of the ammonium cations in the polymers affected stability, reactivity, and enantioselectivity, which is consistent with the hypothesis that the cationic moieties in the polymer support interact with cluster as an exohedral protecting shell, thereby influencing their catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Incorporation of New Benzofulvene Derivatives Into Polymers to Give New NLO Materials

The need for fast electro-optic switches and modulators for optical communication, and laser frequency conversion has created a demand for new second-order non-linear optical materials. One approach to produce such materials is to align chromophores with large molecular hyperpolarizabilities in polymers. Recently fulvenes and benzofulvenes which contain electron donating groups have been shown to exhibit large second-order non-linear optical properties. The resonance structures shown below suggest that intramolecular charge transfer (ICT) should be favorable in omega - (hydroxyphenyl)benzofulvenes and even more favorable in omega-omega - (phenoxy)benzofulvenes because of the enhanced donor properties of the O group. This ICT should lead to enormously enhanced second-order hyperpolarizability. We have prepared all three new omega - (hydroxyphenyl)benzofulvenes by the condensation of indene with the appropriate hydroxyaryl aldehyde in MeOH or MeOH/H2O under base catalysis. In a similar fashion we have prepared substituted benzofulvenes with multipal donor groups. Preliminary studies show that some of our benzofulvene derivatives exhibit second order harmonic generation (SHG). Measurements were carried out by preparing host-guest polymers. The results of our work on benzofulvene derivatives in host-guest polymers when covalently bonded in the polymer will be described.

Bowens, Andrea D.↗
DOE OSTI2020

Electron-Transfer Activation of Thiophene

The research supported by contract FG02-90ER14146 from the U.S. Department of Energy to Thomas B. Rauchfuss is summarized. Seven research themes are described. The work on thiophenes identified pathways for desulfurization that are initiated by electron transfer or hydrolysis. Using similar half-sandwich platforms, a large family of molecular cyanometallate cages were prepared. These cages exhibit host-guest behavior, with a notable affinity for cesium ions. A series of investigations made pioneering contributions to the understanding of the catalytic properties of the hydrogenase enzymes. Work on molecular metal sulfides focused on elucidating hydrogen activation pathways, relevant to the corresponding reactions that are invoked for metal sulfide heterogeneous catalysts. The theme of proton-activated catalysis was continued with the elucidation of the effects of Bronsted acids and oxidation on inducing H2 activation by metal-amides. The proton-activation theme was shown to be a powerful vehicle for upgrading bio-derives substrates including sugars. The project concluded with emphasis on developing ligand platforms that facilitate the use of earth-abundant metals in homogeneous catalysis.

09 BIOMASS FUELS↗