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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 OSTI2020

Catalytic Reactions by Heterobimetallic Carbonyl Complexes with Polar Metal–Metal Interactions

Abstract Heterobinuclear catalysts capable of bimetallic cooperative bond activation provide an alternative pathway to approach the discovery of novel and unique reactivity and selectivity in catalytic transformations, complementing more traditional mononuclear precious metal catalysts. This review summarizes recent advances in homogenous catalysis using heterobimetallic carbonyl catalysts with polar metal–metal interactions. 1 Introduction 2 Hydrogenation and Hydrofunctionalization 3 Carbonylation and Carboxylation 4 Oxidative Transformations 5 Conclusion and Outlook

Chemistry↗
DOE OSTI2022

Dimethyl Carbonate: Review of Synthesis Routes and Catalysts Used

This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed. The major challenges associated with the conversion of CO2 to DMC are the low yields, low DMC selectivity, and thermodynamic limitations (alcohol carbonylation) of reversible reactions with low equilibrium constants. This occurs mainly due to the highly stable carbon dioxide molecules. The development of novel catalysts with high yields and high selectivity needs to be studied to overcome these technical challenges. In addition, to enhance the DMC yield, the use of dehydrating agents for water removal from the reaction mixture is recommended and discussed in detail in this article. This review critically examines the different catalysts used by investigators, along with their respective operating conditions and suitability in applications for the commercial synthesis of CO2-based DMC.

10 SYNTHETIC FUELS↗
DOE OSTI2023

Optimizing the Synthetic Potential of O 2 : Implications of Overpotential in Homogeneous Aerobic Oxidation Catalysis

Molecular oxygen is the quintessential oxidant for organic chemical synthesis, but many challenges continue to limit its utility and breadth of applications. Extensive historical research has focused on overcoming kinetic challenges presented by the ground-state-triplet electronic structure of O 2 and the various reactivity and selectivity challenges associated with reactive oxygen species derived from O 2 reduction. This Perspective will analyze thermodynamic principles underlying catalytic aerobic oxidation reactions, borrowing concepts from the study of the oxygen reduction reaction (ORR) in fuel cells. This analysis is especially important for "oxidase"-type liquid-phase catalytic aerobic oxidation reactions, which proceed by a mechanism that couples two sequential redox half-reactions: (1) substrate oxidation, and (2) oxygen reduction, typically affording H 2 O 2 or H 2 O. The catalysts for these reactions feature redox potentials that lie between the potentials associated with the substrate oxidation and oxygen reduction reactions, and changes in the catalyst potential lead to variations in effective overpotentials for the two half reactions. Catalysts that operate at low ORR overpotential retain more thermodynamic driving force for the substrate oxidation step, enabling O 2 to be used in more challenging oxidations. While catalysts that operate at high ORR overpotential have less driving force available for substrate oxidation, they often exhibit different or improved chemoselectivity relative to the high-potential catalysts. The concepts are elaborated in a series of case studies to highlight their implications for chemical synthesis. Examples include comparisons of (a) NO x /oxoammonium and Cu/nitroxyl catalysts, (b) high-potential quinones and amine oxidase biomimetic quinones, and (c) Pd aerobic oxidation catalysts, with or without NO x cocatalysts. In addition, we show how reductive activation of O 2 provides a means to access potentials not accessible with conventional oxidase-type mechanisms. Altogether, this analysis highlights the central role of catalyst overpotential in guiding the development of aerobic oxidation reactions.

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

Support for U.S. Participants at the 18 th International Congress on Catalysis

The 18 th International Congress on Catalysis (ICC) was held Lyon, France on July 14-19, 2024. It provided a premier technical gathering in surface and organometallic catalysis, industrial homogeneous and heterogeneous catalysis, electrocatalysis, photocatalysis, and catalysis in condensed media. This meeting brough together participants from academia, industry, and national laboratories. The organization that overseed this meeting was the Council of the International Congress on Catalysis. This international committee has over 27 signature countries. The United States is represented in the Council of the International Congress on Catalysis through two permanent representatives. These representatives are elected by the Board of Directors of the North American Catalysis Society (NACS), an organization which coordinates and overseas the activities of 12 largely autonomous clubs within the United States, Canada, and Mexico. The critical importance of catalysis is reflected by the fact that 25-30% of all manufactured goods in the United States involve at least one catalytic step. Because advances in a large number of catalytic processes, which are crucial to U.S. interests, were presented at this meeting, it was important to ensure participation from both the U.S. academic and the industrial sectors.

02 PETROLEUM↗
DOE OSTI2023

Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks

Polyolefin plastics are widely used due to their low cost and outstanding properties, but their environmental persistence presents a major societal challenge. Polyhydroxyalkanoates (PHA) are biodegradable substitutes for polyolefins, but their high cost and thermal instability are impediments to their widespread application. Here we report a series of methylated polyhydroxybutyrates, poly(3-hydroxy-2-methylbutyrate)s, which are structurally inspired by natural PHAs. The cis homopolymers exhibit tacticity-independent crystallinity, which allows for the discovery of high-melting, thermally stable and mechanically tough copolymers, and a full range of polyolefin-like properties can be further achieved by tailoring the cis/trans ratio of the repeating units. Moreover, these materials can be synthesized from inexpensive carbon monoxide and 2-butene feedstocks, and they can be chemically recycled or upcycled at their end of life. As a result, the versatile properties, abundant feedstocks and end-of-life utility of this family of polyesters will enable a powerful platform for the discovery of sustainable alternatives to polyolefin plastics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Direct Observation of Elusive (DTBM‐SEGPHOS)CuH Monomer Enables Mechanistic Insights Into Hydrocupration, Aggregation, and Dynamics of Alkene Functionalization Catalysis

The bulky diphosphine DTBM-SEGPHOS is widely employed in CuH-catalyzed transformations as it provides remarkably active catalyst systems. The transient (DTBM-SEGPHOS)CuH monomer (LCuH) is the often-invoked active species. However, its instability has prevented spectroscopic characterization and mechanistic elucidation, hindering mechanistic understanding. We report low-temperature NMR spectroscopic characterization of LCuH, enabling quantitative kinetic analysis of the stoichiometric hydrocupration and catalytic hydroboration of cyclopentene, as well as the structural identification of two CuH clusters. LCuH inserts cyclopentene at −43°C, reaffirming its high reactivity toward olefins. LCuH deactivates to form L 2 Cu 3 H 3 and L 2 Cu 4 H 4 clusters, in which LCuH dimerization initiates aggregation. Kinetic analysis of reactions of unactivated alkenes indicates that competing on-cycle alkene hydrocupration and LCuH dimerization impact performance, as catalyst deactivation and turnover occur on comparable timescales. Structure–activity analysis using atomistic simulations shows that the steric profile of DTBM-SEGPHOS increases the CuH dimerization barrier by ∼7.7 kcal mol−1 compared to that of SEGPHOS, rationalizing the unique ability of DTBM-SEGPHOS to stabilize a reactive monomer for hydrocupration of broader alkene substrates. These findings illustrate the fundamental design principle that steric control of aggregation governs CuH catalyst performance, explaining both the exceptional activity of (DTBM-SEGPHOS)CuH and the limitations imposed by competing deactivation.

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

Dehydrogenation of 1-Phenylethanol Catalyzed by Nickel(II)diphosphine Complexes

Catalytic efficacy of the nickel(II)-diphosphine systems in the dehydrogenation of 1-phenylethanol to acetophenone under acceptorless conditions was investigated. Steric and electronic factors of the phosphine ligands were found to play an important role in the catalysis, while the nature of the base used and the reaction conditions, viz. time, temperature, and stoichiometry, have also shown major influence. Based on the preliminary analysis, a homogeneous pathway, perhaps involving nickel hydride species, was proposed. Due to the gradual disintegration of the catalytic species, deterioration of catalytic activity was observed resulting into low to moderate conversions. Among the series of catalysts examined, the highest conversion of 52% was exhibited by the catalyst C4, dichloro(1,2-bis(diphenylphosphino)ethane)nickel(II) (5 mol%), when loaded with 50 mol% of sodium ethoxide in toluene at 120 °C.

1,2 bis(alkyl/arylphosphino) alkane. homogeneous c↗
DOE OSTI2023

Homogeneous versus MOF-supported catalysis: a direct comparison of catalytic hydroboration with Ni tripodal P 3 E (E = Si, Ge) complexes

The MOF material NU-1000 was employed to host Ni tripodal complexes prepared from new organometallic precursors [HNi(κ 4 (E,P,P,P)-E(o-C 6 H 4 CH 2 PPh 2 ) 3 ], E = Si (Ni-1), Ge (Ni-2). The new heterogeneous catalytic materials, Ni-1@NU-1000 and Ni-2@NU-1000, show the advantages of both homogeneous and heterogeneous catalysts. Finally, they catalyze the hydroboration of aldehydes and ketones more efficiently than the homogeneous Ni-1 and Ni-2, under aerobic conditions and show recyclability.

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

Advances in supramolecular host-mediated reactivity

Since the trailblazing discoveries of Lehn, Cram and Pedersen, supramolecular chemistry has established itself as a cornerstone of organic chemistry. Supramolecular hosts offer defined microenvironments that mimic the active sites of enzymes, utilizing specific host–guest interactions to enable remarkable rate enhancements and product selectivity. The development of a diverse array of self-assembled hosts, coupled with the increased demand for shorter and greener synthetic routes, have spurred significant progress in the field of supramolecular catalysis. This Review Article covers recent advances in the field, ranging from novel organic reactivity aided by supramolecular hosts to catalytic cooperation between hosts and organometallic compounds or metal nanoparticles. Furthermore, strides have also been made in the synthetic application of these hosts in site-selective substrate modifications and challenging photochemical reactions. These efforts have enabled the incorporation of non-covalent macromolecular catalysis in natural product syntheses, evidencing their unique advantages as a synthetic tool, and their powerful potential for practical applications.

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

Determining the Overpotential of Electrochemical Fuel Synthesis Mediated by Molecular Catalysts: Recommended Practices, Standard Reduction Potentials, and Challenges

Molecular catalysts capable of performing electrochemical transformations are frequently utilized in the synthesis of fuels. A common benchmark for evaluating catalysts for electrochemical reactions is overpotential (η) and minimizing η remains an active goal in catalysis. This Review details approaches for the determination of thermodynamic potentials for common fuel-forming reactions and for the determination of electrochemical overpotential, and underscores the need to employ methods that enable meaningful comparisons between molecular catalysts. Strategies for minimizing overpotential while maintaining high activity are highlighted.

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

Increasing Ligand Denticity and Stability for a Water Oxidation Electrocatalyst using P(V) as Connecting Element

Carboxylate complexes have risen to prominence in the field of water oxidation catalysis. Here for the first time we use the higher valence of phosphinates [P(V)] relative to that of carboxylates [C(IV)] to increase ligand denticity. We describe the synthesis and characterization of a new dianionic pentadentate ligand, bcpq 2− that contains a tridentate 2,2’-bipyridine-6-carboxylato moiety, in addition to a 6’-phosphinato substituent that acts as fourth ligand and bears a side arm containing a quinoline, the fifth ligand. The new bcpq ligand allows formation of [Ru(II)(bcpq)(L)] (2 a–b, L=picoline or isoquinoline) and in preliminary results, of a Co(II) complex. NMR spectroscopy, X-ray diffraction, cyclic voltammetry, differential pulse and square wave voltammetry were used to characterize 2 a–b, with 2 b being characterized more extensively as a catalyst. Bulk electrolysis over 15 h at pH 7 was also used, showing that 2 b gave 100±5 % faradaic efficiency and remained completely homogeneous, whereas 1 b was no longer homogeneous; this comparison conclusively shows the advantage of the added denticity in the electrocatalytic context. Replacing carboxylate with P(V) phosphinate with an added arm may be used in other ligand systems to enhance the durability of homogeneous catalysts.

14 SOLAR ENERGY↗
DOE OSTI2020

2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

The reactivity of Ni(II) and Pd(II) olefin polymerization catalysts can be enhanced by introduction of electron-withdrawing substituents on the supporting ligands rendering the metal centers more electrophilic. Reported here is a comparison of ethylene polymerization activity of a classical salicyliminato nickel catalyst substituted with the powerful electron-withdrawing 2,4,6-triphenylpyridinium (trippy) group to its’ –CF3 analog. The trippy substituent is substantially more electron-withdrawing (σmeta = 0.63) than the trifluoromethyl group (σmeta = 0.43) which results in a ca. 8-fold increase in catalytic turnover frequency. An additional advantage of trippy is its’ high steric bulk relative to the trifluoromethyl group. This feature results in a four-fold increase in polymer molecular weight due to enhanced retardation of chain transfer. Here, a significant increase in catalyst lifetime is observed as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Rhodium‐Catalyzed Oxidative Alkenylation of Naphthalene: Factors That Influence Reaction at the β‐ versus α‐Position

The catalyst precursor [(η 2 -C 2 H 4 ) 2 Rh(μ-OAc)] 2 and in situ oxidant Cu(OPiv) 2 (OPiv = t-BuCOO – ) convert naphthalene and olefins (i.e., ethylene and propylene) to alkenylnaphthalenes. Under all reaction conditions tested, the functionalization is selective for the β-position of naphthalene with the highest observed β:α ratio >20:1. The β-selectivity is catalyst controlled, but oxidant identity, ethylene pressure, and olefin identity influence the ratio of β-alkenylation to α-alkenylation. The concentration of HOPiv and naphthalene do not have an effect on the β:α ratio under the reaction conditions tested. Arenes similar to naphthalene (i.e., o-xylene and 1,2,3,4-tetrahydronaphthalene) give quantitative selectivity for alkenylation at the position β to the substituent. Using propylene as the olefin for naphthalene alkenylation, the β:α ratio is 32(7):1. and the anti-Markovnikov to Markovnikov ratio is 16(2):1.

Alkenes↗
DOE OSTI2024

Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization

Abstract Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon‐supported single atom catalysts focused on nitrogen‐doped carbons, which, unlike classic carbon materials, have a fairly well‐defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting‐edge analytical methods.

Vidal, Mathieu↗
DOE OSTI2021

Site-Selective Real-Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L-Edge X-Ray Absorption Spectroscopy

Here, time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [Ir III (ppy) 2 (bpy)] + photosensitizer, in combination with triethylamine as a sacrificial reductant and Fe 3 (CO) 12 as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale and restricted active space self-consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.

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

Systematic Influence of Electronic Modification of Ligands on the Catalytic Rate of Water Oxidation by a Single-Site Ru-Based Catalyst

Catalytic water oxidation is an important process for the development of clean energy solutions and energy storage. Despite the significant number of reports on active catalysts, systematic control of the catalytic activity remains elusive. In this study, descriptors are explored that can be correlated with catalytic activity. [Ru(tpy)(pic) 2 (H 2 O)](NO 3 ) 2 and [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 (where tpy=2,2': 6',2“-terpyridine, EtO-tpy=4'-(ethoxy)-2,':6',2”-terpyridine, pic=4-picoline) are synthesized and characterized by NMR, UV/Vis, EPR, resonance Raman, and X-ray absorption spectroscopy, and electrochemical analysis. Addition of the ethoxy group increases the catalytic activity in chemically driven and photocatalytic water oxidation. Thus, the effect of the electron-donating group known for the [Ru(tpy)(bpy)(H 2 O)] 2+ family is transferable to architectures with a tpy ligand trans to the Ru-oxo unit. Under catalytic conditions, [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 displays new spectroscopic signals tentatively assigned to a peroxo intermediate. In conclusion, reaction pathways were analyzed by using DFT calculations. [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 is found to be one of the most active catalysts functioning by a water nucleophilic attack mechanism.

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

Sulfonate Group Improves the Solubility and Electrocatalytic Performance of Ru‐Based bda‐ and pda‐Type Water Oxidation Catalysts under Neutral Conditions

Four ruthenium water oxidation catalysts that bear carboxylate and sulfonate groups in the active site have been synthesized and analyzed for their catalytic activity. Here, the sulfonate‐containing catalysts show higher electrochemical activity in pH 7 phosphate buffer with 4 times larger catalytic current, improved durability with sacrificial oxidant, and increased solubility compared to similar species containing two carboxylate groups. Density functional theory calculations suggest that the sulfonate group provides a more favorable geometry for water nucleophilic attack, which is both the energetically most favorable mechanism calculated and the experimentally predicted mechanism under electrochemical conditions. Further experimental studies have been performed to show that under certain conditions catalysts can perform well electrochemically under pH conditions as low as 1.6 and that various structural components can greatly change solubility and catalytic operation.

14 SOLAR ENERGY↗
DOE OSTI2026

Novel insight into the kinetics of amide bond glycolysis for nylon-6 depolymerization

Chemical recycling of nylon-6 to short-chain oligomers and monomer ε-caprolactam via catalytic glycolysis is a potential solution for plastic waste remediation. Here, in this work, the kinetics of amide bond glycolysis (with ethylene glycol) in nylon-6 and the model compound N-phenethyl-3-phenylpropanamide (M1) were evaluated at 473 K in the presence of the cyclic amidine catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene. Rates of polymer glycolysis were determined by the time-dependent shift in molecular weight distribution, whereas rates of M1 glycolysis were determined using liquid chromatography. The similarity of the first-order rate constants for glycolysis of nylon-6 and M1 at 473 K with 0.03 M amidine catalyst (5 mol% relative to amide bonds), 1.22 × 10 −5 s −1 and 2.18 × 10 −5 s −1 , respectively, confirmed the suitability of M1 as a model compound for nylon-6 glycolysis. Similar rates of glycolysis in the presence of other cyclic amidine catalysts as well as sodium methoxide revealed little influence of base strength. Glycolysis rates were unexpectedly non-linear in catalyst loading and deactivation occurred with long reaction times, presumably by non-selective decomposition of products as detected by liquid chromatography.

Depolymerization rate and rate constant↗