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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Hydrogenation of CO2 at Room Temperature and Low Pressure with a Cobalt Tetraphosphine Catalyst

Large-scale implementation of carbon neutral energy sources such as solar and wind will require the development of energy storage mechanisms. The hydrogenation of CO2, a potent greenhouse gas, into formic acid or methanol could function as means to store energy in a chemical bond. Here we report hydrogenation of CO2 to formate under low pressure conditions using a Co(I) tetraphosphine complex, [Co(L3)(CH3CN)]BF4, where L3 = 1,5-diphenyl-3,7-bis(diphenylphosphino)-propyl)-1,5-diaza-3,7-diphosphacyclooctane. [Co(L3)(CH3CN)]+ (0.31 mM) catalyzes CO2 hydrogenation with an initial turnover frequency (TOF) of 150(20) h-1 at 25 °C, 1.7 atm of a 1:1 mixture of H2 and CO2, and 0.6 M tBuTMG (2-tert-Butyl-1,1,3,3-tetramethylguanidine). This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Burgess, Samantha A.↗
DOE OSTI2019

Electrocatalytic Hydrogen Production by a Nickel Complex Containing a Tetradentate Phosphine Ligand

A nickel complex has been synthesized that contains the P4N2 ligand, a tetradendate phosphine ligand with two pendant amines in the ligand backbone. The rigidly square planar Ni(P4N2)2+ complex is an active electrocatalyst for reduction of protons to hydrogen. Using N,N-dimethylformamidium as the acid in wet acetonitrile solution, Ni(P4N2)2+ displays a turnover frequency of 1.6 × 106 s–1, which is among the fastest rates reported for any molecular electrocatalyst. This high catalytic rate comes at the cost of a 1200 mV overpotential at the catalytic half wave potential. The Ni(II) state of the catalyst was found to be stable under strongly acidic conditions, with only trace decomposition observed over two weeks in the presence of 0.1 M trifluoromethanesulfonic acid. The catalyst was less stable in the Ni(0) state due to the inability of the rigid P4N2 ligand to adopt a tetrahedral geometry. Using variable scan rate cyclic voltammetry, a first order rate constant of ~1 s–1 was measured for dissociation of a phosphine from Ni(0), which is proposed to be a key step for determining the lifetime of the catalyst during electrolysis. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.

Klug, Christina↗
DOE OSTI2017

Understanding the Relationship Between Kinetics and Thermodynamics in CO 2 Hydrogenation Catalysis

Linear free-energy relationships have been identified that link the kinetic activity for catalytic hydrogenation of CO2 to formate with the thermodynamic driving force for the rate-limiting steps of catalysis. Cobalt and rhodium bis(diphosphine) complexes with different hydricities (G°H-), acidities (pKa), and free energies for H2 addition (G°H2) were examined. Catalytic CO2 hydrogenation was studied under 1.8 and 20 atm of pressure (1:1 CO2:H2) at room temperature in tetrahydrofuran with a spread of turnover frequencies (TOF) ranging from 0 to 74,000 h-1. The catalysis was followed by 1H and 31P NMR in real time under all conditions to yield information about the rate determining step. Catalysts exhibiting the highest activities were found to have hydride transfer and hydrogen addition steps that were each downhill by approximately 6 to 7 kcal/mol, and the deprotonation step was thermoneutral. The research by M.S.J., A.M.A., E.S.W., and J.C.L. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The research by E.B.H., M.L.H., and M.T.M. (X-ray crystallography, synthesis) was 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. The authors thank Dr. Samantha A. Burgess for assistance in collecting cyclic voltammetry data. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

carbon dioxide↗
DOE OSTI2012

On the Reaction Mechanism of Acetaldehyde Decomposition on Mo(110)

The strong Mo-O bond strength provides promising reactivity of Mo-based catalysts for the deoxygenation of biomass-derived oxygenates. Combining the novel dimer saddle point searching method with periodic spin-polarized density functional theory calculations, we investigated the reaction pathways of a acetaldehyde decomposition on the clean Mo(110) surface. Two reaction pathways were identified, a selective deoxygenation and a nonselective fragmentation pathways. We found that acetaldehyde preferentially adsorbs at the pseudo 3-fold hollow site in the η2(C,O) configuration on Mo(110). Among four possible bond (β-C-H, γ-C-H, C-O and C-C) cleavages, the initial decomposition of the adsorbed acetaldehyde produces either ethylidene via the C-O bond scission or acetyl via the β-C-H bond scission while the C-C and the γ-C-H bond cleavages of acetaldehyde leading to the formation of methyl (and formyl) and formylmethyl are unlikely. Further dehydrogenations of ethylidene into either ethylidyne or vinyl are competing and very facile with low activation barriers of 0.24 and 0.31 eV, respectively. Concurrently, the formed acetyl would deoxygenate into ethylidyne via the C-O cleavage rather than breaking the C-C or the C-H bonds. The selective deoxygenation of acetaldehyde forming ethylene is inhibited by relatively weaker hydrogenation capability of the Mo(110) surface. Instead, the nonselective pathway via vinyl and vinylidene dehydrogenations to ethynyl as the final hydrocarbon fragment is kinetically favorable. On the other hand, the strong interaction between ethylene and the Mo(110) surface also leads to ethylene decomposition instead of desorption into the gas phase. This work was financially supported by the National Advanced Biofuels Consortium (NABC). Computing time was granted by a user project (emsl42292) at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). This work was financially supported by the National Advanced Biofuels Consortium (NABC). Computing time was granted by a user project (emsl42292) at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). The EMSL is a U.S. Department of Energy (DOE) national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and supported by the DOE Office of Biological and Environmental Research. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Incorporating Peptides in the Outer Coordination Sphere of Bio-inspired Electrocatalysts for Hydrogen Production

Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh2NR2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in developing an outer coordination sphere for this class of complexes that can mimic the outer coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh2NPh2)2]2+ complex in acetonitrile solution with turnover frequencies (TOF) for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulphonic acid and 135-1000 s-1 in the presence of triflic acid salt of protonated dimethylformamide, with moderately low overpotentials, ~0.3 V. The addition of small amounts of water result in rate increases of 5-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution whereby the dipeptide tail interacts with the nickel center. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR2NR’2)2]2+ molecular catalytic core to begin to mimic the multifunctional outer coordination sphere of enzymes. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

08 HYDROGEN↗
DOE OSTI2011

[Ni(PPh2NC6H4X2)2]2+ Complexes as Electrocatalysts for H2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates

A series of mononuclear nickel(II) bis(diphosphine) complexes [Ni(PPh2NPhX2)2](BF4)2 (PPh2NPhX2 = 1,5-di(para¬-X-phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane; X = OMe, Me, CH2P(O)(OEt)2, Br, and CF3) have been synthesized and characterized. X-ray diffraction studies reveal that [Ni(PPh2NPhMe2)2](BF4)2 and [Ni(PPh2NPhOMe2)2](BF4)2 are tetracoordinate with distorted square planar geometries. The Ni(II/I) and Ni(I/0) redox couples of each complex are electrochemically reversible in acetonitrile (0.2 M tetraethylammonium tetrafluoroborate) with potentials that are increasingly cathodic as the electron-donating character of X is increased. All of these complexes are efficient electrocatalysts for hydrogen production, with rates generally increasing as the electron-donating character of X is decreased. Catalytic studies using 2,6-dichloroanilinium triflate (2,6-Cl2AnH+OTf , pKaMeCN = 5.0) 4-cyanoanilinium tetrafluoroborate (4-CNAnH+OTf , pKaMeCN = 7.0) and protonated dimethylformamide ([(DMF)H]+OTf , pKaMeCN = 6.1) reveal that turnover frequencies do not correlate with substrate acid pKa values, but are highly dependent on the acid structure, with this effect being related to substrate size. Addition of water is shown to dramatically increase catalytic rates for all catalysts. With [Ni(PPh2NPhCH2P(O)(OEt)22)2](BF4)2 using [(DMF)H]+OTf as acid and with added water, a turnover frequency of 1850 s-1 was obtained. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

08 HYDROGEN↗
DOE OSTI2011

Comproportionation of Cationic and Anionic Tungsten Complexes Having an N -Heterocyclic Carbene Ligand To Give the Isolable 17-Electron Tungsten Radical CpW(CO) 2 (IMes) •

A series consisting of a tungsten anion, radical and cation, supported by the N-heterocyclic carbene IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and spanning formal oxidation states W(0), W(I) and W(II), has been synthesized, isolated, and characterized. Reaction of the hydride CpW(CO)2(IMes)H with KH and 18 crown 6 gives the tungsten anion [CpW(CO)2(IMes)]-[K(18 crown 6)]+. The crystal structure of this complex shows that the K+ interacts not only with the oxygen atoms in the crown ether, but also with the carbonyl oxygens. The electrochemical oxidation of [CpW(CO)2(IMes)]- in acetonitrile is fully reversible (E½ = -1.65 V vs Cp2Fe+•/0) at all scan rates, indicating that CpW(CO)2(IMes)• is a persistent radical. Hydride transfer from CpW(CO)2(IMes)H to Ph3C+PF6 affords [cis-CpW(CO)2(IMes)(MeCN)]+PF6 . Comproportionation of [CpW(CO)2(IMes)]- with [CpW(CO)2(IMes)(MeCN)]+ gives the 17-electron tungsten radical CpW(CO)2(IMes)•. This complex shows paramagnetically shifted resonances in 1H NMR spectra and has been characterized by IR spectroscopy, low-temperature EPR spectroscopy, and X-ray diffraction. CpW(CO)2(IMes)• is very stable with respect to disproportionation and dimerization. NMR studies of degenerate electron transfer between CpW(CO)2(IMes)• and [CpW(CO)2(IMes)]- are reported. DFT calculations were carried out on CpW(CO)2(IMes)H, as well as on related complexes bearing NHC ligands with N,N´ substituents Me [CpW(CO)2(IMe)H] or H [CpW(CO)2(IH)H] to compare to the experimentally studied IMes complexes with mesityl substituents. These calculations reveal W H homolytic bond dissociation energies (BDEs) to decrease with increasing steric bulk of the NHC ligand, from 67 for CpW(CO)2(IH)H to 64 for CpW(CO)2(IMe)H to 63 kcal/mol for CpW(CO)2(IMes)H. The calculated spin density at W for CpW(CO)2(IMes)• is 0.63. The W radicals CpW(CO)2(IMe)• and CpW(CO)2(IH)• are calculated to form weak W W bonds. The weakly bonded complexes [CpW(CO)2(IMe)]2 and [CpW(CO)2(IH)]2, are predicted to have W-W BDEs of 6 and 18 kcal/mol, respectively, and to dissociate readily to the W-centered radicals CpW(CO)2(IMe)• and CpW(CO)2(IH)•. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Direct Conversion of Bio-ethanol to Isobutene on Nanosized ZnxZryOz Mixed Oxides with Balanced Acid–Base Sites

Bio-mass conversion has attracted increasing research interests to produce bio-fuels with bio-ethanol being a major product. Development of advanced processes to further upgrade bio-ethanol to other value added fuels or chemicals are pivotal to improving the economics of biomass conversion and deversifying the utilization of biomass resources. In this paper, for the first time, we report the direct conversion of bio-ethanol to isobutene with high yield (~83%) on a multifunctional ZnxZryOz mixed oxide with a dedicated balance of surface acid-base properties. This work illustrates the significance of rational design of a multifunctional mixed oxide catalyst for one step bio-ethanol conversion to a value-added intermediate, isobutene, for chemical and fuel production. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

09 BIOMASS FUELS↗
DOE OSTI2011

Electrocatalytic Oxidation of Formate by [Ni(P R 2 N R' 2 ) 2 (CH 3 CN)] 2+ Complexes

New [Ni(P R 2 N R` 2 ) 2+ (CH 3 CN)] 2+ complexes with R = Ph, R` = 4-MeOPh; R = Cy, R` = Ph and a mixed ligand [Ni(P R 2 N R` 2 )(P R`` 2 N R` 2 )] 2+ with R = Cy, R` = Ph, R`` = Ph have been synthesized and characterized by single crystal X-ray crystallography. These complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2 , protons, and electrons with rates which are first order in catalyst and in formate at formate concentrations below approximately 0.05 M. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 s -1 to 12.5 s -1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. A mechanistic scheme is proposed which involves an initial nickel complex bound <1-OC(O)H followed by a rate limiting hydride transfer step. An acetate complex demonstrating the η 1 -OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single crystal X-ray crystallography. The pendant amines have been demonstrated to be essential for this electrocatalytic activity as no activity toward formate was found for the similar [Ni(depe) 2 ][BF 4 ] 2+ (depe = diethylphosphinoethane) complex. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2012

Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H 2

The iron complexes CpFe(PPh2NBn2)Cl (1-Cl), CpFe(PPh2NPh2)Cl (2-Cl), CpFe(PPh2C5)Cl (3-Cl) (where PPh2NBn2 is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, PPh2NPh2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane, and PPh2C5 is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction studies. These chloride derivatives are readily converted to the corresponding hydride complexes CpFe(PPh2NBn2)H (1-H), CpFe(PPh2NPh2)H (2-H), CpFe(PPh2C5)H (3-H)] and H2 complexes [CpFe(PPh2NBn2)(H2)]BArF4, [1-H2]BArF4, (where BArF4 is B[(3,5-(CF3)2C6H3)4]-), [CpFe(PPh2NPh2)(H2)]BArF4, [2-H2]BArF4, and [CpFe(PPh2C5)(H2)]BArF4, [3-H2]BArF4 as well as [CpFe(PPh2NBn2)(CO)]BArF4, [1-CO]BArF4. Structural studies are reported for [1-H2]BArF4, 1-H, 2-H, and [1-CO]BArF4. The conformations adopted by the chelate rings of the PPh2NBn2 ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BArF4 is 2.848 Å, considerably shorter than the sum of the van der Waals radii of N and C atoms. Experimental and theoretical studies of H/D exchange by the complexes [1-H2]+, [2-H2]+, and [3-H2]+ indicate that the relatively rapid exchange observed for [1-H2]+ and [2-H2]+ compared to [3-H2]+ is consistent with intramolecular heterolytic cleavage of H2 mediated by the pendant amine. These mononuclear FeII dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe] hydrogenase required for H-H bond formation and cleavage. We thank the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences, for support of this research. S.C. (DFT computations) and M. J. O. (NMR experiments) were supported by 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, under FWP 56073. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

59 BASIC BIOLOGICAL SCIENCES↗