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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 OSTI2023

Bioconversion of Homogeneous Linear C-Lignin to Polyhydroxyalkanoates

Here, the bioconversion of homogeneous linear catechyl lignin (C-lignin) to polyhydroxyalkanoates (PHA) was examined for the first time in this study. C-lignins from vanilla, euphorbia, and candlenut seed coats (denoted as C1, C2, and C3, respectively) varied in their molecular structures, which showed different molecular weight distributions, etherification degrees, and contents of hydroxyl groups. A notable amount of nonetherified catechol units existed within C1 and C2 lignins, and these catechol units were consumed during fermentation. These results suggested that the nonetherified catechol structure was readily converted by Pseudomonas putida KT2440. Since the weight-average molecular weight of C2 raw lignin was 26.7% lower than that of C1, the bioconversion performance of C2 lignin was more outstanding. The P. putida KT2440 cell amount reached the maximum of 9.3 × 10 7 CFU/mL in the C2 medium, which was 37.9 and 82.4% higher than that in the C1 and C3 medium, respectively. Accordingly, PHA concentration reached 137 mg/L within the C2 medium, which was 41.2 and 149.1% higher than the C1 and C3 medium, respectively. Overall, C-lignin, with a nonetherified catechol structure and low molecular weight, benefits its microbial conversion significantly.

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

Sawtooth lattice multiferroic BeCr 2 O 4 : Noncollinear magnetic structure and multiple magnetic transitions

Noncollinear magnetic structures and multiple magnetic phase transitions in a sawtooth lattice antiferromagnet consisting of Cr 3+ are experimentally identified in this work, thereby proposing the scenario of magnetism-driven ferroelectricity in a sawtooth lattice. The title compound, BeCr 2 O 4 , displays three magnetic phase transitions at low temperatures—at T N1 ≈ 7.5 K, at T N2 ≈ 25 K, and at T N3 ≈ 26 K—revealed through magnetic susceptibility, specific heat, and neutron diffraction in this work. These magnetic phase transitions are found to be influenced by externally applied magnetic fields. Isothermal magnetization curves at low temperatures below the magnetic transitions indicate the antiferromagnetic nature of BeCr 2 O 4 with two spin-flop-like transitions occurring at H c1 ≈ 29 kOe and H c2 ≈ 47 kOe. Our high-resolution x-ray and neutron diffraction studies, performed on single crystal and powder samples, unambiguously determined the crystal structure as orthorhombic Pbnm. By performing the magnetic superspace group analysis of the neutron diffraction data at low temperatures, the magnetic structure in the temperature range T N3,N2 < T < T N1 is determined to be the polar magnetic space group P21nm. 1' (00g) 0s0s with a cycloidal magnetic propagation vector k 1 = (0, 0, 0.090 (1)) . The magnetic structure in the newly identified phase below T N1 is determined as P21/b.1' [b] (00 g) 00s with the magnetic propagation vector k 2 = (0, 0, 0.908 (1)). Finally, the cycloidal spin structure determined in our work is usually associated with electric polarization, thereby making BeCr 2 O 4 a promising multiferroic belonging to the sparsely populated family of sawtooth lattice antiferromagnets.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Compositions and textures of relic forsterite in carbonaceous and unequilibrated ordinary chondrites

The compositions and textures of olivines in equilibrated ordinary chondrites, C1, C2, and C3 meteorites are described. The olivines are classified by color into blue, red, or dark olivines. The characteristic features of blue olivines are examined. It is observed that the texture of the olivine: (1) forms cores in single olivine grains; (2) shows subhedral to euhedral boundaries against rim olivines; (3) rarely contains inclusions; (4) has embayments containing olivines similar to that of the rim; and (5) occurs within chondrules. The mode of formation for blue olivines, the relation between blue olivine and high temperature compounds, and modifications in the features of blue olivines are analyzed. It is noted that the olivine is a product of condensation, has been modified by additions of olivine formed from a liquid, and that these olivines represent relic grains that are similar to olivines found in cosmic particles and in cores of some deep sea particles.

Steele, I. M.↗
DOE OSTI2024

CsO x Nanostructures on Au(111): Morphology- and Size-dependent Activity for the Water–Gas Shift Reaction

Alkali oxides are typically used as promoters of heterogeneous catalysts for the water–gas shift (WGS; H 2 O + CO → H 2 + CO 2 ) reaction. On Au(111), CsO x exhibits diverse nanostructures at varying coverages, as revealed by scanning tunneling microscopy. Clusters of cesium oxide (Cs 2 O 2 ) nucleate at elbow sites of the Au(111) herringbone when θ Cs is less than 0.1 ML. Subsequently, these clusters transform into two-dimensional (2D) islands (Cs 2 O, Cs 2 O 2 , CsO 2 ) as the cesium coverage increases (θ Cs > 0.1 ML). Both types of CsO x nanostructures enable the WGS process on Au(111). The highest activity was seen for the cesium oxide clusters which facilitated the partial dissociation of water and binding of CO. The CO ads and OH ads groups were not strongly bound and probably reacted to yield a short-lived HOCO intermediate that led to gaseous H 2 and CO 2 . The 2D islands of CsO x also enabled the WGS but their efficiency was reduced due to the formation of cesium hydroxide compounds (limiting mobility of OH groups) and the generation of CO 3 and C species (blocking of active centers). The fact that the performance of the CsO x /Au(111) catalysts changed dramatically with variations in the chemical properties of the CsO x nanostructures indicates that the alkali oxide was an integral part of the active phase, playing a central role in the activation and conversion of the reactants. To attach the label of “promoter” to CsO x is a simplification that does not help in the design and optimization of catalysts for C1 chemistry. In conclusion, to achieve a rational design, one must consider the structural and chemical properties of the alkali oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2023

One-bond 13 C– 13 C spin-coupling constants in saccharides: a comparison of experimental and calculated values by density functional theory using solid-state 13 C NMR and X-ray crystallography

Methyl aldohexopyranosides were 13 C-labeled at contiguous carbons, crystallized, and studied by single-crystal X-ray crystallography and solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy to examine the degree to which density functional theory (DFT) can calculate one-bond 13C–13C spin-coupling constants ( 1 J CC ) in saccharides with sufficient accuracy to permit their use in MA'AT analysis, a newly-reported hybrid DFT/NMR method that provides probability distributions of molecular torsion angles in solution (Zhang et al., J. Phys. Chem. B, 2017, 121, 3042–3058; Meredith et al., J. Chem. Inf. Model., 2022, 62, 3135–3141). Experimental 1 J CC values in crystalline samples of the doubly 13 C-labeled compounds were measured by solid-state 13 C NMR and compared to those calculated from five different DFT models: (1) 1 J CC values calculated from single structures identical to those observed in crystalline samples by X-ray crystallography (all atom refinement); (2) 1 J CC values calculated from the single structures in (1) but after Hirshfeld atom refinement (HAR); (3) 1 J CC values calculated from the single structures in (1) after DFT-optimization of hydrogen atoms only; and (4 and 5) 1 J CC values calculated in rotamers of torsion angle θ 2 (C1–C2–O2–O2H) or ω(C4–C5–C6–O6) from which either specific or generalized parameterized equations were obtained and used to calculate 1 J CC values in the specific θ 2 or ω rotamers observed in crystalline samples. Good qualitative agreement was observed between calculated 1 J CC values and those measured by solid-state 13 C NMR regardless of the DFT model, but in no cases were calculated 1 J CC values quantitative, differing (over-estimated) on average by 4–5% from experimental values. These findings, and those reported recently from solution NMR studies (Tetrault et al., J. Phys. Chem. B 2022, 126, 9506–9515), indicate that improvements in DFT calculations are needed before calculated 1 J CC values can be used directly as reliable constraints in MA'AT analyses of saccharides in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2020

The Production and Potential Detection of Hexamethylenetetramine-Methanol in Space

Numerous laboratory studies of astrophysical ice analogues have shown that their exposure to ionizing radiation leads to the production of large numbers of new, more complex compounds, many of which are of astrobiological interest. We show here that the irradiation of astrophysical ice analogues containing H2O, CH3OH, CO, and NH3 yields quantities of hexamethylenetetramine-methanol (hereafter HMT-methanol; C7N4H14O) that are easily detectible in the resulting organic residues. This molecule differs from simple HMT, which is known to be abundant in similar ice photolysis residues, by the replacement of a peripheral H atom with a CH2OH group. As with HMT, HMT-methanol is likely to be an amino acid precursor. HMT has tetrahedral (T(d)) symmetry, whereas HMT-methanol has C1 symmetry. We report the computed expected infrared spectra for HMT and HMT-methanol obtained using ab initio quantum chemistry methods and show that there is a good match between the observed and computed spectra for regular HMT. Since HMT-methanol lacks the high symmetry of HMT, it produces rotational transitions that could be observed at longer wavelengths, although establishing the exact positions of these transitions may be challenging. It is likely that HMT-methanol represents an abundant member of a larger family of functionalized HMT molecules that may be present in cold astrophysical environments.

Materese, Christopher K.↗
DOE OSTI2021

Diversifying Isoprenoid Platforms via Atypical Carbon Substrates and Non-model Microorganisms

Isoprenoid compounds are biologically ubiquitous, and their characteristic modularity has afforded products ranging from pharmaceuticals to biofuels. Isoprenoid production has been largely successful in Escherichia coli and Saccharomyces cerevisiae with metabolic engineering of the mevalonate (MVA) and methylerythritol phosphate (MEP) pathways coupled with the expression of heterologous terpene synthases. Yet conventional microbial chassis pose several major obstacles to successful commercialization including the affordability of sugar substrates at scale, precursor flux limitations, and intermediate feedback-inhibition. Now, recent studies have challenged typical isoprenoid paradigms by expanding the boundaries of terpene biosynthesis and using non-model organisms including those capable of metabolizing atypical C1 substrates. Conversely, investigations of non-model organisms have historically informed optimization in conventional microbes by tuning heterologous gene expression. Here, we review advances in isoprenoid biosynthesis with specific focus on the synergy between model and non-model organisms that may elevate the commercial viability of isoprenoid platforms by addressing the dichotomy between high titer production and inexpensive substrates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Computational Predictions of the Hydrolysis of 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN)

Hydrolysis is a common transformation reaction that can affect the environmental fate of many organic compounds. In this study, three proposed mechanisms of alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroaniline (DNAN) were investigated with plane-wave density functional theory (DFT) combined with ab initio and classical molecular dynamics (AIMD/MM) free energy simulations, Gaussian basis set DFT calculations, and correlated molecular orbital theory calculations. Most of the computations in this study were carried out using the Arrows web based tools. For each mechanism: Meisenheimer complex formation, nucleophilic aromatic substitution, and proton abstraction reaction energies and activation barriers were calculated for the reaction at each relevant site. For TNT, it was found that the most kinetically favorable first hydrolysis steps involve Meisenheimer complex formation by attachment of OH$^{-}$ at the C1 and C3 arene carbons and proton abstraction from the methyl group. The nucleophilic aromatic substitution reactions at the C2 and C4 arene carbons were found to be thermodynamically favorable. However, the calculated activation barriers were slightly lower than previous studies, but still found to be $\Delta$G$^{\ddagger} \approx 18$ kcal/mol using PBEo AIMD/MM free energy simulations, suggesting the reactions are not kinetically significant. For DNAN, the barriers of nucleophilic aromatic substitution were even greater ($\Delta$G$^{\ddagger} > 29$ kcal/mol PBEo AIMD/MM). Further, the most favorable hydrolysis reaction for DNAN was found to be a two-step process in which the hydroxyl first attacks the C1 carbon to form a Meisenheimer complex at the C1 arene carbon C1-(OCH$_3$)OH$^{-}$, subsequently, the methoxy anion (-OCH$_3$) at the C1 arene carbon dissociates and the proton shuttles from the C1-OH to the dissociated methoxy group, resulting in methanol and an aryloxy anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

C-13/C-12 ratio in methane from the flooded Amazon forest

The C1-C4 hydrocarbon concentrations and the C-13/C-12 ratio in CH4 detected in air samples collected in the Amazon region (3.5 deg S latitude and 5.9 deg W longitude) are analyzed. It is observed that the CH4 concentrations of each sample are enhanced over the background concentration for remote locations, and the C-13/C-12 ratio in this biogenic methane is depleted in C-13 relative to atmospheric CH4. It is concluded, from the C2-C4 hydrocarbon data, that minor yields of C2-C4 hyrocarbons are released coincident with CH4; however, the minor yields do not contribute to the regionally enhanced concentrations of hydrocarbons found in Amazonia and the global atmosphere release of C2-C4 compounds.

Tyler, Stanley C.↗
DOE OSTI2023

Exotic Reaction Dynamics in the Gas-Phase Preparation of Anthracene (C 14 H 10 ) via Spiroaromatic Radical Transients in the Indenyl–Cyclopentadienyl Radical–Radical Reaction

The gas-phase reaction between the 1-indenyl (C 9 H 7 •) and the cyclopentadienyl (C 5 H 5 •) radical has been investigated for the first time using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. Soft photo-ionization with tunable vacuum ultraviolet photons afforded for the isomer-selective identification of the production of phenanthrene, anthracene, and benzofulvalene (C 14 H 10 ). The classical theory prevalent in the literature proposing that radicals combine only at their specific radical centers is challenged by our discovery of an unusual reaction pathway that involves a barrierless combination of a resonantly stabilized hydrocarbon radical with an aromatic radical at the carbon atom adjacent to the traditional C1 radical center; this unconventional addition is followed by substantial isomerization into phenanthrene and anthracene via a category of exotic spiroaromatic intermediates. Furthermore, this result leads to a deeper understanding of the evolution of the cosmic carbon budget and provides new methodologies for the bottom-up synthesis of unique spiro-aromatics that may be relevant for the synthesis of more complex aromatic carbon skeletons in deep space.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2020

The Old, Unique C1 Chondrite Flensburg – Insight Into the First Processes of Aqueous Alteration, Brecciation, and the Diversity of Water-Bearing Parent Bodies and Lithologies

On September 12, 2019 at 12:49:48 (UT) a bolide was observed by hundreds of eye-witnesses from the Netherlands, Germany, Belgium, Denmark and the UK. One day later a small meteorite stone was found by accident in Flensburg. The presence of short-lived cosmogenic radionuclides with half-lives as short as 16 days proves the recent exposure of the found object to cosmic rays in space linking it clearly to the bolide event. An exceptionally short exposure time of ∼5000 years was determined. The 24.5 g stone has a fresh black fusion crust, a low density of <2 g/cm(exp 3), and a magnetic susceptibility of logχ = 4.35 (χ in 10−9 m(exp 3)/kg). The rock consists of relict chondrules and clusters of sulfide and magnetite grains set in a fine-grained matrix. The most abundant phases are phyllosilicates. Carbonates (∼3.9 vol.%) occur as calcites, dolomites, and a Na-rich phase. The relict chondrules (often surrounded by sulfide laths) are free of anhydrous silicates and contain abundant serpentine. Lithic clasts are also surrounded by similar sulfide laths partly intergrown with carbonates. Mn-53-Cr-53 ages of carbonates in Flensburg indicate that brecciation and contemporaneous formation of the pyrrhotite-carbonate intergrowths by hydrothermal activities occurred no later than 4564.6 ± 1.0 Ma (using the angrite D'Orbigny as the Mn-Cr age anchor). This corresponds to 2.6 ± 1.0 or 3.4 ± 1.0 Ma after formation of CAIs, depending on the exact absolute age of CAIs. This is the oldest dated evidence for brecciation and carbonate formation, which likely occurred during parent body growth and incipient heating due to decay of Al-26. In the three oxygen isotope diagram, Flensburg plots at the 16O-rich end of the CM chondrite field and in the transition field to CV-CK-CR chondrites. The mass-dependent Te isotopic composition of Flensburg is slightly different from mean CM chondrites and is most similar to those of the ungrouped C2 chondrite Tagish Lake. On the other hand, Ti-50 and Cr-54 isotope anomalies indicate that Flensburg is similar to CM chondrites, as do the ∼10 wt.% H2O of the bulk material. Yet, the bulk Zn, Cu, and Pb concentrations are about 30% lower than those of mean CM chondrites. The He, Ne, and Ar isotopes of Flensburg show no solar wind contribution; its trapped noble gas signature is similar to that of CMs with a slightly lower concentration of Ne(sub tr)-20. Based on the bulk H, C, and N elemental abundances and isotopic compositions, Flensburg is unique among chondrites, because it has the lightest bulk H and N isotopic compositions of any type 1 or 2 chondrite investigated so far. Moreover, the number of soluble organic compounds in Flensburg is even lower than that of the brecciated CI chondrite Orgueil. The extraordinary significance of Flensburg is evident from the observation that it represents the oldest chondrite sample in which the contemporaneous episodes of aqueous alteration and brecciation have been preserved. The characterization of a large variety of carbonaceous chondrites with different alteration histories is important for interpreting returned samples from the OSIRIS-REx and Hayabusa 2 missions.

C1 chondrite↗
DOE OSTI2023

The synthesis of novel lanthanum hydroxyborate at extreme conditions

The novel structure of lanthanum hydroxyborate La 2 B 2 O 5 (OH) 2 was synthesized by the reaction of partially hydrolyzed lanthanum and boron oxide in a diamond anvil cell under high-pressure/high-temperature (HPHT) conditions of 30 GPa and ~2,400 K. The single-crystal X-ray structure determination of the lanthanum hydroxyborate revealed: P$\overline{3}$c1 , a = 6.555(2) Å, c = 17.485(8) Å, Z = 6, R 1 = 0.056. The three-dimensional structure consists of discrete planar BO 3 groups and three crystallographically different La ions: one is surrounded by 9, one by 10, and one by 12 oxygen anions. The band gap was estimated using ab initio calculations to be 4.64 eV at ambient pressure and 5.26 eV at 30 GPa. The current work describes the novel HPHT lanthanum hydroxyborate with potential application as a deep-ultraviolet birefringent material.

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

Anisotropic magnetism and electronic structure of trigonal EuAl 2 Ge 2 single crystals

Understanding the interplay between magnetic and electronic degrees of freedom is of profound recent interest in different Eu-based magnetic topological materials. Here, we studied the magnetic and electronic properties of the layered Zintl-phase compound EuAl 2 Ge 2 crystallizing in the trigonal CaAl 2 Si 2 -type structure. We report zero-field neutron diffraction, temperature T - and magnetic-field H-dependent magnetic susceptibility χ(T, H), isothermal magnetization M(T, H), heat capacity C p (T, H), and electrical resistivity ρ(T, H) measurements, together with T-dependent angle-resolved photoemission spectroscopy (ARPES) measurements complemented with first-principle calculations. EuAl 2 Ge 2 undergoes second-order A-type antiferromagnetic (AFM) ordering below T N = 27.5(5) K, with the Eu moments (Eu 2+ , S = 7/2) aligned ferromagnetically in the ab plane while these layers are stacked antiferromagnetically along the c axis. The critical fields at which all moments become parallel to the field are 37.5(5) and 52.5(5) kOe for H ∥ ab and H ∥ c, respectively. The H = 0 magnetic structure consists of trigonal AFM domains associated with ab-plane magnetic anisotropy and a field-induced reorientation of the Eu spins in the domains is also evident at T = 2 K below the critical field H c1 = 2.5(1) kOe. The ρ(T) measurements reveal metallic behavior transforming into a slight resistivity increase on cooling towards T N . A pronounced loss of spin-disorder scattering is observed below T N . The ARPES results show that EuAl 2 Ge 2 is metallic both above and below T N , and the Fermi surface is anisotropic with two hole pockets at the zone center and one small electron pocket at each M point. In the AFM phase, we directly observe folded bands in ARPES due to the doubling of the magnetic unit cell along the c axis with an enhancement of quasiparticle weight due to the complex change in the coupling between the magnetic moments and itinerant electrons on cooling below T N . The observed electronic structure is well reproduced by first-principle calculations, which also predict the presence of nontrivial electronic states near the Fermi level in the AFM phase with Z 2 topological numbers 1;(000)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

TBS FROST Data from 2023 at SGP C1

The FROST provides chemical analysis of four time-resolved sorbent samples on a LECO GCxGC Bench Time of Flight Mass Spectrometer, using a Gerstel MPS Thermal Desorption System. Samples collected via FROST can be analyzed on one of two Sandia National Laboratories' instruments. One instrument will provide ultra-high mass spectrometer resolution (up to four decimal points or m/z data) and can be used for identification of true unknowns. Data can include suspected formulas of species not included in any current mass spectra database. This instrument also has a low limit of detection of known species (tens of femtogram range). The second instrument can provide an order of magnitude lower limits of detection (into the single-digit femtogram range) for known species currently in mass spectra databases. This system is also more resilient to environmental samples that contain higher levels of moisture.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

CO 2 electro-reduction on Cu 3 P: Role of Cu(I) oxidation state and surface facet structure in C 1 -formate production and H 2 selectivity

We report the catalytic activity and mechanism of copper(I) phosphide, Cu 3 P, with predominant [00Ι] facet exposure for the electrochemical reduction of CO 2 (CO 2 RR) to formic acid. Crystalline nanosheets of this compound that show a preferential [00Ι] facet orientation exhibit undiminished CO 2 RR activity after 16 hours with full retention of crystal structure and surface chemical speciation and no detectable corrosion. In contrast to the range of products formed on Cu metal, CuO, and Cu 2 O, the CO 2 RR on Cu 3 P [00Ι] produces mainly hydrogen and formate as the sole carbon product in KHCO 3 electrolyte. Analysis of the Cu 3 P [00Ι] facet by HAADF-STEM was used to determine the surface lattice structure, while both XPS and Auger spectroscopies were used to determine the surface chemical speciation from the kinetic energies of ionized electrons. The presented analysis identifies isolated trigonal CuP 3 sites on the Cu 3 P[00Ι]-Cu 3 P 3 terminated surface and the Cu(I) oxidation state as precursor to the active catalyst. The CO 2 RR selectivity to formate and the higher turnover rate for H 2 production on the [00Ι] facet allows a structure-activity analysis and chemical mechanism to be proposed. Formation of a surface hydride at isolated *H-CuP 3 sites is proposed as the catalytic site in forming both H 2 and formate, while the long Cu—Cu separation retards forming C-C coupling products. In conclusion, these results disprove previously published claims of Cu(I) oxidation state as a sufficient criterion to promote CO 2 RR to C 2+ products, show that stronger bonded hydrides, *H-CuP 3 on Cu 3 P, favor production of the C1 product formate over all other carbon products, and predict that stronger formate binding (bidentate) is needed for CO 2 RR currents to compete with H 2 production.

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

Alpha ketoacid decarboxylases: Diversity, structures, reaction mechanisms, and applications for biomanufacturing of platform chemicals and fuels

In living cells, alpha-ketoacid decarboxylases (KDCs, EC 4.1.1.-) are a class of enzymes that convert alpha-ketoacids into aldehydes through decarboxylation. These aldehydes serve as either drop-in chemicals or precursors for the biosynthesis of alcohols, carboxylic acids, esters, and alkanes. These compounds play crucial roles in cellular metabolism and fitness and the bioeconomy, facilitating the sustainable and renewable biomanufacturing of platform chemicals and fuels. This review explores the diversity and classification of KDCs, detailing their structures, mechanisms, and functions. We highlight recent advancements in repurposing KDCs to enhance their efficiency and robustness for biomanufacturing. Additionally, we present modular KDC-dependent metabolic pathways for the microbial biosynthesis of aldehydes, alcohols, carboxylic acids, esters, and alkanes. Lastly, we discuss recent developments in the modular cell engineering technology that can potentially be applied to harness the diversity of KDC-dependent pathways for biomanufacturing platform chemicals and fuels.

09 BIOMASS FUELS↗
DOE OSTI2021

Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties

Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗