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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Effects of Phosphonate Structures on Brine–Biotite Interactions under Subsurface Relevant Conditions

Phosphonates have been widely used as scale inhibitors in energy-related subsurface operations, where their performance is greatly affected by interactions with rocks and minerals. However, information about commonly used phosphonate scale inhibitor–shale interactions is limited. In this study, using Fe-bearing mica (biotite) as a model phyllosilicate mineral, the effects of three common phosphonates, namely, iminodi(methylene)phosphonate (IDMP), nitrilotris(methylene)phosphonate (NTMP), and diethylenetriaminepenta(methylene)phosphonate (DTPMP), were studied at 95 °C and 102 atm CO2. During the experiments (0–70 h), IDMP remained stable, while NTMP and DTPMP were degraded and released phosphate, formate, and new phosphonates with smaller molecular weights. As a result of the differences in complexation capability, IDMP, with the fewest phosphonate functional groups, promoted biotite dissolution mainly through surface complexation and DTPMP, with the most functional groups, promoted biotite dissolution mainly through aqueous complexation. Furthermore, the presence of phosphonates enhanced secondary precipitation of P-, Fe-, and Al-bearing minerals, and their phosphonate structures affected the morphologies, phases, and distributions of secondary precipitates. Owing to phosphonate–biotite interactions (mainly as a result of surface adsorption), the biotite surfaces became much more hydrophilic. This study provides new insights into structure-dependent phosphonate–mineral interactions, and the results have important implications for the safety and efficiency of energy-related subsurface operations.

bio-inspired, mechanical behavior, carbon sequestr↗
DOE OSTI2013

Dynamic Evolution of Cement Composition and Transport Properties under Conditions Relevant to Geological Carbon Sequestration

Assessing the possibility of CO{sub 2} leakage is one of the major challenges for geological carbon sequestration. Injected CO{sub 2} can react with wellbore cement, which can potentially change cement composition and transport properties. In this work, we develop a reactive transport model based on experimental observations to understand and predict the property evolution of cement in direct contact with CO{sub 2}-saturated brine under diffusion-controlled conditions. The model reproduced the observed zones of portlandite depletion and calcite formation. Cement alteration is initially fast and slows down at later times. This work also quantified the role of initial cement properties, in particular the ratio of the initial portlandite content to porosity (defined here as φ), in determining the evolution of cement properties. Portlandite-rich cement with large φ values results in a localized “sharp” reactive diffusive front characterized by calcite precipitation, leading to significant porosity reduction, which eventually clogs the pore space and prevents further acid penetration. Severe degradation occurs at the cement–brine interface with large φ values. This alteration increases effective permeability by orders of magnitude for fluids that preferentially flow through the degraded zone. The significant porosity decrease in the calcite zone also leads to orders of magnitude decrease in effective permeability, where fluids flow through the low-permeability calcite zone. The developed reactive transport model provides a valuable tool to link cement–CO{sub 2} reactions with the evolution of porosity and permeability. It can be used to quantify and predict long-term wellbore cement behavior and can facilitate the risk assessment associated with geological CO{sub 2} sequestration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

Fragmentation Energetics of Clusters Relevant to Atmospheric New Particle Formation

The exact mechanisms by which small clusters form and grow in the atmosphere are poorly understood, but this process may significantly impact cloud condensation nuclei number concentrations and global climate. Sulfuric acid is the key chemical component to new particle formation, but basic species such as ammonia are also important. However, few laboratory experiments address the kinetics or thermodynamics of acid and base incorporation into small clusters. This work utilizes a Fourier transform ion cyclotron resonance mass spectrometer equipped with surface-induced dissociation (FTICR-SID) to investigate time- and collision energy-resolved fragmentation of positively charged ammonium bisulfate clusters. Critical energies for dissociation are obtained from Rice-Ramsperger-Kassel-Marcus/Quasi-Equilibrium Theory (RRKM/QET) modeling of the experimental data and are compared to quantum chemical calculations of the thermodynamics of cluster dissociation. Fragmentation of ammonium bisulfate clusters occurs by two pathways: 1) a two-step pathway whereby the cluster sequentially loses ammonia followed by sulfuric acid and 2) a one-step pathway whereby the cluster loses an ammonium bisulfate molecule. Experimental critical energies for loss of an ammonia molecule and loss of an ammonium bisulfate molecule are higher than the thermodynamic values. If cluster growth is considered the reverse of cluster fragmentation, these results require the presence of an activation barrier to describe the incorporation of ammonia into small acidic clusters and suggest that kinetically (i.e. diffusion) limited growth should not be assumed. An important corollary is that models of atmospheric NPF should be revised to consider activation barriers to individual chemical steps along the growth pathway.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2020

3 d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni( t-Bu bpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV–Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3 d-d rather than 3 MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1 H NMR techniques, supporting that this 3 d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3 d-d state was determined to lie ~0.5 eV (12 kcal/mol) above the ground state. Because the 3 d-d state features a weak Ni–aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni–aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Characterization of an Fe≡N–NH 2 intermediate relevant to catalytic N 2 reduction to NH 3

The ability of certain transition metals to mediate the reduction of N 2 to NH 3 has attracted broad interest in the biological and inorganic chemistry communities. Early transition metals such as Mo and W readily bind N 2 and mediate its protonation at one or more N atoms to furnish M(N x H y ) species that can be characterized and, in turn, extrude NH 3 . By contrast, the direct protonation of Fe–N 2 species to Fe(N x H y ) products that can be characterized has been elusive. In this paper, we show that addition of acid at low temperature to [(TPB)Fe(N 2 )][Na(12-crown-4)] results in a new S = 1/2 Fe species. EPR, ENDOR, Mössbauer, and EXAFS analysis, coupled with a DFT study, unequivocally assign this new species as [(TPB)Fe≡N–NH 2 ] + , a doubly protonated hydrazido(2–) complex featuring an Fe-to-N triple bond. This unstable species offers strong evidence that the first steps in Fe-mediated nitrogen reduction by [(TPB)Fe(N 2 )][Na(12-crown-4)] can proceed along a distal or “Chatt-type” pathway. Finally, a brief discussion of whether subsequent catalytic steps may involve early or late stage cleavage of the N–N bond, as would be found in limiting distal or alternating mechanisms, respectively, is also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co 4 O 4 : Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co 4 O 4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t 2g -based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co 4 O 4 . Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co 4 O 4 to CoM 3 O 4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E 0 over hundreds of mVs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

Incorporation of Mn into an established water oxidation catalyst based on a Co(III) 4 O 4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo 3 O 4 (OAc) 5 py 3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc - ligand for Cl - (1-Cl), NO 3 - (1-NO 3 ), and pyridine ([1-py] + ). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [Mn IV Co III 3 ]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo 3 O 4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

A mononuclear nonheme iron(IV)–amido complex bearing a tetraamido macrocyclic ligand, [(TAML)Fe IV (NHTs)] - (1), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)–imido complex, [(TAML)FeV(NTs)]- (2), and fully characterized using various spectroscopies. We then investigated (1) the pK a of 1, (2) the reaction of 1 with a carbon-centered radical, and (3) the H atom abstraction reaction of 1. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)–amido complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗