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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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Molecular Catalysts with Diphosphine Ligands Containing Pendant Amines

Pendant amines play an invaluable role in chemical reactivity, especially for molecular catalysts based on Earth-abundant metals. As inspired by [FeFe]-hydrogenases, which contain a pendant amine positioned for cooperative bifunctionality, synthetic catalysts have been developed to emulate this multifunctionality through incorporation of a pendant amine in the second coordination sphere. Cyclic diphosphine ligands containing two amines serve as the basis for a class of catalysts that have been extensively studied and used to demonstrate the impact of a pendant base. These 1,5-diaza-3,7-diphosphacyclooctanes, now often referred to as “P 2 N 2 ” ligands, have profound effects on the reactivity of many catalysts. The resulting [Ni(P R 2 N R ´ 2 ) 2 ] 2+ complexes are electrocatalysts for both the oxidation and production of H 2 . Achieving the optimal benefit of the pendant amine requires that it has suitable basicity and is properly positioned relative to the metal center. In addition to the catalytic efficacy demonstrated with [Ni(P R 2 N R ´ 2 )2] 2+ complexes for the oxidation and production of H2, catalysts with diphosphine ligands containing pendant amines have also be demonstrated for a variety of metals for many different reactions, both in solution and immobilized on surfaces. Here, the impact of pendant amines in catalyst design has been demonstrated and continues to expand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

In situ x-ray absorption investigations of a heterogenized molecular catalyst and its interaction with a carbon nanotube support

A highly active heterogenized molecular CO 2 reduction catalyst on a conductive carbon support is investigated to identify if its improved catalytic activity can be attributed to strong electronic interactions between catalyst and support. The molecular structure and electronic character of a [Re +1 (tBu-bpy)(CO) 3 Cl] (tBu-bpy = 4,4'-tert-butyl-2,2'-bipyridine) catalyst deposited on multiwalled carbon nanotubes are characterized using Re L 3 -edge x-ray absorption spectroscopy under electrochemical conditions and compared to the homogeneous catalyst. The Re oxidation state is characterized from the near-edge absorption region, while structural changes of the catalyst are assessed from the extended x-ray absorption fine structure under reducing conditions. Chloride ligand dissociation and a Re-centered reduction are both observed under applied reducing potential. The results confirm weak coupling of [Re(tBu-bpy)(CO) 3 Cl] with the support, since the supported catalyst exhibits the same oxidation changes as the homogeneous case. However, these results do not preclude strong interactions between a reduced catalyst intermediate and the support, preliminarily investigated here using quantum mechanical calculations. Thus, our results suggest that complicated linkage schemes and strong electronic interactions with the initial catalyst species are not required to improve the activity of heterogenized molecular catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Compartmentalisation of molecular catalysts for nonorthogonal tandem catalysis

The development of nonorthogonal tandem catalysis enables the use of a combination of arbitrary catalysts to rapidly synthesize complex products in a substainable, efficient, and timely manner. The key is to compartmentalise the molecular catalysts, thereby overcoming inherent incompatibilities between individual catalysts or reaction conditions. This tutorial review analyses the development of the past two decades in the field of nonorthogonal tandem catalysis with an emphasis on compartmentalisation strategies. Here, we highlight design principles of functional materials for compartmentalisation and suggest future directions in the field of nonorthogonal tandem catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photoelectrochemical CO 2 Reduction to CO Enabled by a Molecular Catalyst Attached to High-Surface-Area Porous Silicon

A high-surface-area p-type porous Si photocathode containing a covalently immobilized molecular Re catalyst is highly selective for the photoelectrochemical conversion of CO 2 to CO. It gives Faradaic efficiencies of up to 90% for CO at potentials of –1.7 V (versus ferrocenium/ferrocene) under 1 sun illumination in an acetonitrile solution containing phenol. Here, the photovoltage is approximately 300 mV based on comparisons with similar n-type porous Si cathodes in the dark. Using an estimate of the equilibrium potential for CO 2 reduction to CO under optimized reaction conditions, photoelectrolysis was performed at a small overpotential, and the onset of electrocatalysis in cyclic voltammograms occurred at a modest underpotential. The porous Si photoelectrode is more stable and selective for CO production than the photoelectrode generated by attaching the same Re catalyst to a planar Si wafer. Further, facile characterization of the porous Si-based photoelectrodes using transmission mode FTIR spectroscopy leads to highly reproducible catalytic performance.

14 SOLAR ENERGY↗
DOE OSTI2022

Restructuring and integrity of molecular catalysts in electrochemical CO 2 reduction

Electrocatalysts that start a reaction as molecules do not always end the reaction as molecules, and even when they do, they might not be molecules during catalysis. In this Perspective, we discuss knowledge learned from the study of Cu-based molecularly structured electrocatalysts––including metal coordination complexes, metal-organic frameworks, single-atom catalysts, and polymeric materials––that restructure under electrochemical CO 2 reduction reactions. Recent reports are summarized with an emphasis on the nature and significance of post-mortem and in situ characterization for the proper identification of active sites. We demonstrate that molecular and material structures determine whether electrocatalysts restructure and how they restructure, that understanding of restructuring processes can help us identify active sites for catalysis, and that this knowledge can be leveraged to design precatalysts that generate highly active catalysts under reaction conditions. In addition, we provide recommended practices for studying the integrity of heterogeneous molecular catalysts during and after CO 2 reduction reactions.

CO2 reduction↗
DOE OSTI2020

Surface-Attached Molecular Catalysts on Visible-Light-Absorbing Semiconductors: Opportunities and Challenges for a Stable Hybrid Water-Splitting Photoanode

Hybrid photoanodes for water-splitting photoelectrochemical cells (WS-PECs) consist of a visible-light-absorbing semiconductor (VLASC) with a molecular water-oxidation catalyst (mWOC) attached, and show great promise for solar fuel generation. In this perspective, we will focus on the less emphasized but crucial subject of stability in these systems. The stability of each component, including the VLASC, the mWOC, and the connection of the two, must individually be considered, as well as how the system functions as a whole. We offer design strategies for each of these parts, as well as some characterization techniques helpful in the study of degradation. Lastly, we propose some future directions for the development of hybrid WS-PEC photoanodes with long-term stability that could be suitable for practical application.

14 SOLAR ENERGY↗
DOE OSTI2022

Molecular Catalyst Synthesis Strategies to Prepare Atomically Dispersed Fe-N-C Heterogeneous Catalysts

We report a strategy to integrate atomically dispersed iron within a heterogeneous nitrogen-doped carbon (N-C) support, inspired by routes for metalation of molecular macrocyclic iron complexes. The N-C support, derived from pyrolysis of a ZIF-8 metal–organic framework, is metalated via solution-phase reaction with FeCl 2 and tributyl amine, as a Brønsted base, at 150 °C. Fe active sites are characterized by 57 Fe Mössbauer spectroscopy and aberration-corrected scanning transmission electron microscopy. The site density can be increased by selective removal of Zn 2+ ions from the N-C support prior to metalation, resembling the transmetalation strategy commonly employed for the preparation of molecular Fe-macrocycles. As a result, the utility of this approach is validated by the higher catalytic rates (per total Fe) of these materials relative to established Fe-N-C catalysts, benchmarked using an aerobic oxidation reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Interfacial Charge Transfer Pathways in Photoelectrochemical H 2 Evolution by a Single-Component Molecular Catalyst on a Conductive Metal Oxide

Dye-sensitized photoelectrosynthesis cells traditionally combine a photosensitizing dye to harvest light and a catalyst to generate chemical fuels on a semiconductor. Here, in this work, a photoactive catalyst capable of both light absorption and fuel formation, [Cp*Ir(4,4′-Y 2 -bpy)Cl][Cl] (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine, Y = CH 2 PO 3 H 2 ), is anchored to a mesoporous tin-doped indium oxide (ITO) electrode and facilitates photoelectrochemical H 2 evolution in water without the need for additional photosensitizers or sacrificial reductants. Spectroelectrochemistry indicates a single-site H 2 evolution mechanism involving charge injection to ITO, in contrast to the bimetallic mechanism observed in solution. Cyclic voltammetry and variable-potential chronoamperometry under illumination probe competing pathways via interfacial electron transfer between the Ir hydride excited state and the conductive ITO electrode. A Marcus theory framework provides reorganization energies for competing interfacial electron transfer pathways from potential-dependent quantum yield measurements. The light-driven H 2 evolution catalysis on conducting oxide proceeds with high Faradaic efficiency and current densities comparable to photoelectrodes utilizing p-type semiconductors. By uncovering the principal electron transfer pathways that govern photocatalytic efficiency, this study establishes design principles for hybrid molecular photoelectrocatalysts.

catalysts↗