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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Controlling Proton Delivery with Catalyst Structural Dynamics

The fastest synthetic molecular catalysts for production and oxidation of H2 emulate components of the active site of natural hydrogenases. The role of controlled structural dynamics is recognized as a critical component in the catalytic performance of many enzymes, including hydrogenases, but is largely neglected in the design of synthetic molecular cata-lysts. In this work, the impact of controlling structural dynamics on the rate of production of H2 was studied for a series of [Ni(PPh2NC6H4-R2)2]2+ catalysts including R = n-hexyl, n-decyl, n-tetradecyl, n-octadecyl, phenyl, or cyclohexyl. A strong correlation was observed between the ligand structural dynamics and the rates of electrocatalytic hydrogen production in acetonitrile, acetonitrile-water, and protic ionic liquid-water mixtures. Specifically, the turnover frequencies correlate inversely with the rates of ring inversion of the amine-containing ligand, as this dynamic process dictates the positioning of the proton relay in the second coordination sphere and therefore governs protonation at either catalytically productive or non-productive sites. This study demonstrates that the dynamic processes involved in proton delivery can be controlled through modifications of the outer coordination sphere of the catalyst, similar to the role of the protein architecture in many enzymes. The present work provides new mechanistic insight into the large rate enhancements observed in aqueous protic ionic liquid media for the [Ni(PPh2NR2)]2+ family of catalysts. The incorporation of controlled structural dynamics as a design parameter to modulate proton delivery in molecular catalysts has enabled H2 production rates that are up to three orders of magnitude faster than the [Ni(PPh2NPh2)]2+complex. The observed turnover frequencies are up to 106 s-1 in acetonitrile-water, and over 107 s-1 in protic ionic liquid-water mixtures, with a minimal increase in overpotential. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, and was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE.

electrocatalysis, structural dynamics↗
DOE OSTI2024

Catalytic Upgrading of Renewable Feedstock (Final Technical Report)

The goal of this DOE-funded project was to investigate the fundamental science related to the development of homogeneous (de)hydrogenation catalysts in order to enable energy-relevant transformations of bio-relevant chemical feedstocks including ethanol. The primary focus was to improve the activity of ethanol upgrading catalysts, specifically informed through mechanistic studies, in order to enable rational design optimization strategies. Following in depth mechanistic studies, targeted reaction optimization approaches included ligand redesign to improve catalyst stability, developing new carbon-carbon bond forming reactions using ethanol as a precursor, and examining photochemically-mediated reactions, ultimately to integrate within other reactor designs such as continuous flow reactors. The high modularity of the catalyst components (ligands) has enabled the preparation and analyses of multiple catalyst precursors. These studies uncovered an unexpectedly beneficial substitution pattern of the ligand structure that led to the development of new catalysts that are the best in class for upgrading ethanol to butanol with a turnover number of 155,890 and a turnover frequency of 12,690 h –1 . In addition to upgrading ethanol to butanol, cascade reaction sequences were developed to form new C-C bonds using ethanol as a bio-relevant feedstock, providing access to platform chemicals from renewable sources. As part of the reaction discovery process, new mechanistic details were uncovered that provided insights into: a) catalyst speciation, b) decomposition pathways, c) carbon monoxide releasing pathways, and d) carbon-carbon and carbon hydrogen bond breaking pathways. Most of these outcomes were previously not known; however, they provide important directions for new catalyst design strategies. Finally, use of high throughput and in situ photochemical reaction analyses enabled detailed studies into changes to the catalyst structure upon irradiation. Irradiation was found to improve hydrogen transfer catalysis, by promoting a ligand dissociation event.

09 BIOMASS FUELS↗
DOE OSTI2026

Polymer Deconstruction and Redesign Strategies for Plastics Recycling

Advancing plastics recycling requires both the selective deconstruction of existing polymers and the design of new materials that enable efficient reuse without loss of performance. This perspective highlights an integrated approach that is rooted in polymer chemistry, catalysis, and process engineering which can enable a circular plastics economy. Here, we outline recent advances in catalytic, solvolytic, and enzymatic pathways for plastic deconstruction, and examine the molecular design principles driving next-generation recyclable-by-design and bio-based polymers. Despite these advances, major knowledge gaps remain in understanding the evolution of polymer morphology and catalyst structure during deconstruction, assessing deconstruction processes with realistic polymers, and offering redesigned polymers with competitive cost and environmental advantage over conventional plastics. United States Department of Energy (U.S. DOE) national laboratories offer unique capabilities to address these challenges through in situ and operando characterization, high-throughput experimentation, environmental studies, technoeconomic and life cycle assessment, scale-up support, and collaboration networks. Advances made in understanding plastic deconstruction mechanisms and structure-property correlations of redesigned polymers inform emerging research directions including autonomous experimentation, real-time feedback-enabled process optimization, and protein engineering for enzymatic depolymerization.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Studying the Durability of Molybdenum Carbide Aerogel as an Electrocatalyst Support for Proton Exchange Membrane Fuel Cells

Carbon-supported platinum nanoparticles (Pt/C) are currently the state-of-the-art catalyst in proton exchange membrane fuel cells (PEMFCs). Unfortunately, the carbon support lacks the ability to stabilize the metal catalyst, as platinum tends to dissolve and agglomerate, significantly compromising the durability. Herein, we synthesized a ceramic material, molybdenum carbide aerogel (MCAG), and utilized it as a Pt support for PEMFCs, as an alternative for conventional carbon supports. N 2 adsorption and XRD analysis showed that the MCAG possesses a combination of high porosity and a well-defined ceramic crystalline structure. The Pt/MCAG system was studied for its electrocatalytic activity toward ORR in a half-cell and demonstrated satisfactory reaction kinetics and electrochemical active surface area, comparable to the commercial Pt/C. For durability examination, an accelerated stress test (AST) in a single cell was conducted with the Pt/MCAG catalyst at the cathode, following the U.S. DOE electrocatalyst AST protocol. Intermediate polarization curves and cyclic voltammograms were recorded over the course of the AST to monitor the aging process. The results indicated that the MCAG support exhibited superior durability in long-term fuel cell operation compared to a carbon support. The Pt/MCAG system demonstrated stable behavior during the progressive stages of the AST, retaining more than 50% of its initial performance by the end of the test, whereas carbon-supported Pt preserved only 30%.

25 ENERGY STORAGE↗
DOE OSTI2014

Highly Active and Stable MgAl2O4 Supported Rh and Ir Catalysts for Methane Steam Reforming: A Combined Experimental and Theoretical Study

In this work we present a combined experimental and theoretical investigation of stable MgAl2O4 spinel-supported Rh and Ir catalysts for the steam methane reforming (SMR) reaction. Firstly, catalytic performance for a series of noble metal catalysts supported on MgAl2O4 spinel was evaluated for SMR at 600-850°C. Turnover rate at 850°C follows the order: Pd > Pt > Ir > Rh > Ru > Ni. However, Rh and Ir were found to have the best combination of activity and stability for methane steam reforming in the presence of simulated biomass-derived syngas. It was found that highly dispersed ~2 nm Rh and ~1 nm Ir clusters were formed on the MgAl2O4 spinel support. Scanning Transition Electron Microscopy (STEM) images show that excellent dispersion was maintained even under challenging high temperature conditions (e.g. at 850°C in the presence of steam) while Ir and Rh catalysts supported on Al2O3 were observed to sinter at increased rates under the same conditions. These observations were further confirmed by ab initio molecular dynamics (AIMD) simulations which find that ~1 nm Rh and Ir particles (50-atom cluster) bind strongly to the MgAl2O4 surfaces via a redox process leading to a strong metal-support interaction, thus helping anchor the metal clusters and reduce the tendency to sinter. Density functional theory (DFT) calculations suggest that these supported smaller Rh and Ir particles have a lower work function than larger more bulk-like ones, which enables them to activate both water and methane more effectively than larger particles, yet have a minimal influence on the relative stability of coke precursors. In addition, theoretical mechanistic studies were used to probe the relationship between structure and reactivity. Consistent with the experimental observations, our theoretical modeling results also suggest that the small spinel-supported Ir particle catalyst is more active than the counterpart of Rh catalyst for SMR. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time was granted by a user proposal at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) located at PNNL. Part of the computational time was provided by the National Energy Research Scientific Computing Center (NERSC).

ab initio molecular dynamics↗
DOE OSTI2018

Where does the sulphur go? Deactivation of a low temperature CO oxidation catalyst by sulphur poisoning

Sulphate formation, occurring preferentially at the CuO/CeOx-ZrOx interface, is responsible for the deactivation of low temperature CO oxidation catalysts. XRD, FTIR and isotope exchange experiments, as well as DFT calculations, reveal the poisoning mechanism of sulphate formation on the CeOx/ZrOx support material. JS, DM, TV and CHFP gratefully acknowledge the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program for the support of their participation in this work. Their studies were performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research, and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. DOE by Battelle under contract number DE-AC05-76RL01830.

Szanyi, Janos↗
DOE OSTI2013

Conversion of Low-Rank Wyoming Coals into Gasoline by Direct Liquefaction

Under the cooperative agreement program of DOE and funding from Wyoming State’s Clean Coal Task Force, Western Research Institute and Thermosolv LLC studied the direct conversion of Wyoming coals and coal-lignin mixed feeds into liquid fuels in conditions highly relevant to practice. During the Phase I, catalytic direct liquefaction of sub-bituminous Wyoming coals was investigated. The process conditions and catalysts were identified that lead to a significant increase of desirable oil fraction in the products. The Phase II work focused on systematic study of solvothermal depolymerization (STD) and direct liquefaction (DCL) of carbonaceous feedstocks. The effect of the reaction conditions (the nature of solvent, solvent/lignin ratio, temperature, pressure, heating rate, and residence time) on STD was investigated. The effect of a number of various additives (including lignin, model lignin compounds, lignin-derivable chemicals, and inorganic radical initiators), solvents, and catalysts on DCL has been studied. Although a significant progress has been achieved in developing solvothermal depolymerization, the side reactions – formation of considerable amounts of char and gaseous products – as well as other drawbacks do not render aqueous media as the most appropriate choice for commercial implementation of STD for processing coals and lignins. The trends and effects discovered in DCL point at the specific features of liquefaction mechanism that are currently underutilized yet could be exploited to intensify the process. A judicious choice of catalysts, solvents, and additives might enable practical and economically efficient direct conversion of Wyoming coals into liquid fuels.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Synergistic effect of polyaniline on stabilizing Pt nanoparticles in PEMFCs†

The stability of Pt nanoparticles on a carbon support is crucial for the lifespan of polymer electrolyte membrane fuel cells as well as other electrocatalysis systems such as electrolyzers. Here we took the approach of utilizing the covalently grafted polyaniline on carbon to stabilize Pt nanoparticles by simultaneously alleviating the particle migration and mitigating the Ostwald ripening, which are two major mechanisms for loss of the catalyst stability. A comprehensive investigation of the stability and performance of Pt catalyst nanoparticles on these supports reveals that the polyaniline can shift the Pt L edge binding energy and the Pt 4f peak energy, leading to the increased redox potential of the Pt nanoparticles and making them more resistant to oxidation. Interestingly, the highest polyaniline density (50 wt%) does not show the best catalyst stability, rather, the second (33 wt%) demonstrates the best catalyst stability among these catalysts. Combining the XPS, XAS and fuel cell stability studies, we concluded that the locations of the Pt nanoparticles over the polyaniline layer on the carbon surface depend on the surface density of the polyaniline over the carbon surface. The Pt nanoparticles in the 50 wt% polyaniline catalyst are wrapped by the polyaniline polymer but do not sit directly on the carbon surface, while Pt nanoparticles in the 33 wt% polyaniline catalyst sit on the carbon surface and are densely surrounded by the polyaniline polymer. The results show that the mass activity loss is 12.5% while the ECSA (electrochemically active surface area) loss is 37.1% after 30k cycles of accelerating stress test for the 33 wt% polyaniline catalyst, far exceeding the DOE 2020 target for MEA (i.e., mass activity loss < 50%, and ECSA loss < 40%). Overall, the polyaniline has a synergistic effect on mitigating the surface migration and slowing down the Ostwald ripening to stabilize the Pt nanoparticles in fuel cells. The novel strategy to stabilize Pt nanoparticles using polyaniline opens a new pathway in the development of highly stable catalysts: relying on the functionalization group on the carbon support, instead of just focusing on the catalyst itself.

Li, Chenzhao↗
DOE OSTI2026

Energy Leaders: The Catalyst for Strategic Energy Management

This study investigates the crucial role energy leaders play in driving strategic energy management (SEM) and accelerating cost savings within a manufacturing organization and consequently, the industrial sector. Whereas energy efficiency can be seen as an innovative business practice with irrefutable cost benefits, its effective implementation requires strategic leadership and a structured approach. This research analyzes data collected from 120 participants representing 71 companies attending the Energy Bootcamp events organized by the U.S. Department of Energy’s (DOE) Better Plants program. The collected data focused on the state of SEM implementation, the presence and responsibilities of energy leaders, and the formation and function of energy teams. The findings reveal a significant gap between the perceived importance of SEM and its actual adoption, highlighting the need for strong leadership to drive behavioral changes by championing energy efficiency initiatives. Results indicate that effective energy leaders possess a diverse skill set, including the ability to secure top management buy-in, foster a culture of energy consciousness, and collaborate across departments. This study emphasizes the importance of empowering energy leaders with clearly defined roles and responsibilities as well as the authority to build and lead cross-functional energy teams. Furthermore, integrating energy management into existing organizational structures and leveraging readily available resources are identified as key factors for successful implementation. This research underscores how dedicated leadership and effective SEM practices help achieve industrial energy efficiency goals, providing practical insights for organizations seeking to improve performance and contribute to a resilient future.

energy leader↗
DOE OSTI2012

Chemistry of Complexes with Transition Metal Heteroatom Bonds: Novel Insertion Chemistry and XH Bond Activation (Final Report)

For roughly 15 years, the Department of Energy, Basic Energy Sciences has supported our studies on a series of new organometallic transformations that form carbon-heteroatom bonds. These studies constitute some of the most cited work in organometallic chemistry over the past decades, including two papers in Science and many papers highlighted in the secondary literature, such as C&EN. This work also includes the synthesis of organic materials with novel electronic properties and collaborative studies to reveal the dynamics of the energy and electron transport within these materials. Finally, this work includes the development of new methods for accelerated catalyst discovery, a general approach to this type of discovery that has become a staple method in all types of industrial laboratories and some academic laboratories. This grant has ended as a result of my move to UC Berkeley. My research supported by DOE will now be a part of the catalysis program at LBNL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Preliminary Examination of Ethanol Fuel Effects on EPA’s R-factor for Vehicle Fuel Economy

The U.S. Department of Energy (DOE) supported a test program from 2007 through 2012 to evaluate the potential impacts of intermediate ethanol blends (also known as mid-level blends) on legacy vehicles and other engines. The purpose of the program was to assess the viability of using intermediate ethanol blends as a contributor to meeting national goals for the use of renewable fuels. Appendix A lists a bibliography of related studies. The catalyst durability program involved aging and emissions testing vehicles on a range of ethanol blends. The study was completed in 2011 and a final report issued shortly after. This report describes a preliminary analysis of the fuel economy data from the catalyst durability study, to determine the proper value for the R factor which is called out in the Code of Federal Regulations (CFR) for computing vehicle fuel economy on the certification cycle. The fuel economy equation that is specified in CFR for gasoline-fuelled vehicles is based on a carbon mass balance (CMB) approach to determine the amount of fuel consumed during the test by measuring the carbon-bearing emissions that are produced; however, it also incorporates a scaling factor (R factor) based on the net heating value of the fuel and the sensitivity of fuel economy to changes in the heating value. The impact of the R factor is a fixed ratio in the resultant fuel economy that is dependent upon fuel properties other than those required for a typical CMB calculation. This equation was put in place in 1988 to correct for differences between certification fuels to address corporate average fuel economy (CAFE) credit issues associated with fuel property variations. The algorithm adjusts the calculated fuel economy to compute what would have been measured had the 1975 certification fuel been used for the test. The R factor was defined as the sensitivity of the fuel economy result to changes in fuel energy content. When R equals 1.0, the fuel economy change exactly tracks the energy density difference between the fuels. If R is less than 1.0, the fuel economy change is smaller than the change in energy density. The R factor was defined to be 0.6 based on tests using 1980s vehicles. Since that time, the Auto/Oil test program has established that the R factor for 1990s vehicles is higher (about 0.93). More recently EPA analyzed the EPAct/V2/E-89 dataset to compute the R factor, resulting in an average of 0.82 to 0.86. It is important to note that the EPAct/V2/E89 test program used the LA92 test cycle, a cycle known to contain more aggressive accelerations than the FTP. To date, EPA has only required emissions and fuel economy testing of gasoline vehicles with a certification fuel that does not contain ethanol. However in 2013 EPA issued a Proposed Rule seeking comment on the establishment of an emissions certification fuel containing ethanol, such as E10 or E15. Calculating modern vehicle fuel economy with the existing CFR equation with an R factor of 0.6 when ethanol blends are used produces significant errors. For the catalyst durability program, a straightforward CMB approach was used to compute fuel economy, thereby allowing a straightforward evaluation of the impact of ethanol content on fuel economy. However, if an ethanol-containing fuel is to become the new certification fuel for light-duty vehicles, consistent application of the CFR equation needs to be considered for the benefit of manufacturers’ CAFE compliance. Analysis of city cycle Federal Test Procedure (FTP) fuel economy test results and fuel analyses from the catalyst durability study indicates that the average R-factor for modern vehicles is very close to unity at about 0.94±0.04. This result is very similar to the results of the 1993 Auto/Oil test program. Future work should examine other drive cycles, and advanced vehicle technologies which may reveal sensitivities to properties other than heating value.

intermediate ethanol blends↗
DOE OSTI2016

Efficient Discovery of Novel Multicomponent Mixtures for Hydrogen Storage: A Combined Computational/Experimental Approach

The objective of the proposed program is to discover novel mixed hydrides for hydrogen storage, which enable the DOE 2010 system-level goals. Our goal is to find a material that desorbs 8.5 wt.% H 2 or more at temperatures below 85°C. The research program will combine first-principles calculations of reaction thermodynamics and kinetics with material and catalyst synthesis, testing, and characterization. We will combine materials from distinct categories (e.g., chemical and complex hydrides) to form novel multicomponent reactions. Systems to be studied include mixtures of complex hydrides and chemical hydrides [e.g. LiNH 2+ NH 3 BH 3 ] and nitrogen-hydrogen based borohydrides [e.g. Al(BH 4 ) 3 (NH 3 ) 3 ]. The 2010 and 2015 FreedomCAR/DOE targets for hydrogen storage systems are very challenging, and cannot be met with existing materials. The vast majority of the work to date has delineated materials into various classes, e.g., complex and metal hydrides, chemical hydrides, and sorbents. However, very recent studies indicate that mixtures of storage materials, particularly mixtures between various classes, hold promise to achieve technological attributes that materials within an individual class cannot reach. Our project involves a systematic, rational approach to designing novel multicomponent mixtures of materials with fast hydrogenation/dehydrogenation kinetics and favorable thermodynamics using a combination of state-of-the-art scientific computing and experimentation. We will use the accurate predictive power of first-principles modeling to understand the thermodynamic and microscopic kinetic processes involved in hydrogen release and uptake and to design new material/catalyst systems with improved properties. Detailed characterization and atomic-scale catalysis experiments will elucidate the effect of dopants and nanoscale catalysts in achieving fast kinetics and reversibility. And, state-of-the-art storage experiments will give key storage attributes of the investigated reactions, validate computational predictions, and help guide and improve computational methods. In sum, our approach involves a powerful blend of: 1) H2 Storage measurements and characterization, 2) State-of-the-art computational modeling, 3) Detailed catalysis experiments, 4) In-depth automotive perspective.

08 HYDROGEN↗
DOE OSTI2014

Multicomponent Protein Cage Architectures for Photocatalysis

The central focus of the work performed under this award has been to develop the bacteriophage P22 viral capsid as a vehicle for the encapsulation of catalyticaly active cargo materials and study their utility towards economic energy harvesting systems. We have demonstrated that the capsid of the bacteriophage P22 can be used to genetically program the assembly and encapsulation of a range of inorganic nanoparticles and protein cargoes. The P22 capsid uses a scaffold protein (SP) to direct the assembly of its coat protein (CP) into icosahedral capsids. By creating a genetic fusion of a desired cargo enzyme or a small peptide that can act as a nucleation site for subsequent NP growth, we have demonstrated the co-assembly of these SP-fusions and CP into stable “nano-reactors”. The cargo is sequestered inside the engineered capsid and can either be used directly as a nanocatalyst or for the nucleation and growth of inorganic or organic nanoparticles or polymers. The synthetic cargos (NP or polymers) were shown to have photocatalytic activity. The time dependent photophysics of a select few of these systems were studied to determine the underlying mechanisms and efficiency of light harversting. Enzyme cargos encapsulated within the P22 were thermally activated catalysts and their kinetic behavior was characterized. During the course of this work we have demonstrated that the method is a robust means to harness biology for materials applications and have initiated work into assembling the P22 nanoreactors into hierarchically ordered materials. The successful implementation of the work performed under this DOE grant provides us with a great deal of knowledge and a library of components to go forward towards the development of bioinspired catalytic materials for energy harvesting.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Dissecting the steps of CO2 reduction: 1. The interaction of CO and CO2 with γ-Al2O3: an in situ FTIR study

The adsorption of CO2 and CO was investigated on a pure γ-Al2O3 support material that has been used for the preparation of Pd and Ru catalysts for the catalytic reduction of CO2. The adsorption of CO2 resulted in the formation of carbonates, bicarbonates and linearly adsorbed CO2 species. The amount and the nature of the adsorbed species were dependent on the annealing temperature of the alumina support. On γ-Al2O3 annealed at 473 K mostly bicarbonates formed, while no adsorbed CO2 was seen on this highly hydroxylated surface. With increasing calcinations temperature, i.e., increasing extent of dehydroxylation, the amounts of both surface nitrates and linear adsorbed CO2 increased, but still the most abundant surface species were bicarbonates. Surface carbonates and adsorbed CO2 can readily be removed from the alumina surface, while bicarbonates are stable to elevated temperatures. The interaction of CO with γ-Al2O3 is much weaker than that of CO2. At room temperatures CO adsorbs only on Lewis acid sites, and can be readily removed by evacuation. At 100 K CO can probe different defect sites on the alumina surface (both Lewis acid sites and surface hydroxyls). Under no conditions we have observed the formation of any carbonates or bicarbonates upon the interaction of CO with the pure alumina support. In co-adsorption experiments CO competes for adsorption sites with the linearly adsorbed CO2 on the 773 K-annealed γ-Al2O3 surface; but it does not result in the desorption of CO2, rather in the increase of weakly-held carbonate production. After the removal of adsorbed CO, CO2 moves back to its original adsorption sites, i.e., Lewis acidic Al3+ centers. The exposure of a CO2-saturated γ-Al2O3 to H2O did not affect any of the adsorbed surface species. The findings of this study will be used to rationalize the results of our ongoing in situ and in operando studies on the reduction of CO2 on supported Pd and Ru catalysts. Acknowledgements: We gratefully acknowledge the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for the support of this work. The synthesis and catalyst pre-treatment portion of the work described in this manuscript was supported by a Laboratory Directed Research and Development (LDRD) project at the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute. J.H.K. also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).

CO and CO2 adsorption↗
DOE OSTI2014

Development of Catalytic Alkylation and Fluoroalkylation Methods

In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands after Fu had published his initial report showing that pybox ligands could successfully catalyze alkyl-alkyl cross-coupling reactions. We found that reaction of (TMEDA)NiMe 2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2, eq 4), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr 2 ] and [Ni(COD) 2 ] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72% isolated) by the precipitation of 1 from THF solvent.

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

Catalytic oxidative coupling of arenes and alkanes: applications for efficient chemical synthesis and for hydrocarbon oligomerization. Progress Report 2016-7. Final report

This is the final report for DE-FG02-08ER15997 with a grant period of 8/15/2008-8/14/2018 (plus 1 year NCE); Program: Basic Energy Sciences; PI: Melanie S. Sanford; co-PI: Adam J. Matzger. The project resulted in 20 publications, 12 supported entirely by this grant and 8 supported substantially by this grant. The overall goals of this project were design catalysts (both homogeneous catalysts and MOF-supported catalysts) to control reactivity and selectivity in energy relevant C–H bond functionalization reactions. The proposed research led to a variety of new catalysts and catalytic processes which are currently finding application in organic synthesis. These efforts were well aligned with the goals of the DOE BES Catalysis Science Program. C–H functionalization reactions have extensive applications in energy-related industries, including petroleum and biofuels processing. The research activities also matched many of the priority areas identified by the Catalysis Science Program, including: investigating problems at the interface of heterogeneous and homogeneous catalysis as a means to derive new catalysts; incorporating 2° interactions to modulate catalyst stability, reactivity, and selectivity; using these new catalysts to tune molecular-level catalytic activity and selectivity; and studying structure-reactivity relationships of inorganic, organic, or hybrid catalytic materials in solution.

02 PETROLEUM↗