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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Unassisted solar-driven water electrolysis as a sustainable source for H 2 is limited by the high overpotential necessary to drive the oxygen evolution reaction (OER). Crude glycerol is an extremely alkaline byproduct of biodiesel synthesis that can be valorized or refined to produce more desirable chemicals. Glycerol can also be directly oxidized on an anode, replacing water oxidation, to reduce the applied cell potential requirements of electrolytic H 2 production or CO 2 reduction. An advantage of oxidizing glycerol in its crude form is the opportunity to valorize it without initial refinement. We describe an approach to replace the OER half-reaction with the sacrificial crude glycerol electrooxidation on a layered Au–Pt–Bi electrocatalyst on a Ni substrate. Compared to compositions with fewer components, the AuPtBi–Ni electrocatalyst improved the duration of performance and reduced the overall cell potential for glycerol electrooxidation in the extreme alkaline solutions representative of crude glycerol. These enhancements facilitated extended, unassisted hydrogen evolution from crude glycerol electrolysis, even under the power of a single-junction silicon solar cell at less than 1 sun illumination. We characterized the oxidation products of crude glycerol electrolysis and the subsequent products formed spontaneously in the electrolyte in the highly alkaline solution. This analysis helps to both identify the stoichiometric limits of glycerol oxidation at the low cell potentials of interest here and to understand the chemical control imparted by electrocatalysis on the ultimate compounds formed in the crude solution. Furthermore, the results for the AuPtBi electrocatalyst show that incorporating crude glycerol oxidation into integrated electrochemical systems can simultaneously simplify their design and significantly improve solar-to-hydrogen rates.

08 HYDROGEN↗
DOE OSTI2023

Two-Step Chemical Looping Cycle for Renewable NH 3 Production Based on Non-Catalytic Co 3 Mo 3 N/Co 6 Mo 6 N Reactions

A two-step solar thermochemical looping cycle based on Co 3 Mo 3 N/Co 6 Mo 6 N reduction/nitridation reactions offers a pathway for green NH 3 production that utilizes concentrated solar irradiation, H 2 O, and air as feedstocks. The NH 3 production cycle steps both derive process heat from concentrated solar irradiation and encompass 1) the reduction of Co 3 Mo 3 N in H 2 to Co 6 Mo 6 N and NH 3 ; and 2) nitridation of Co 6 Mo 6 N to Co 3 Mo 3 N with N 2 . Co 3 Mo 3 N reduction/nitridation reactions are examined at different H 2 and/or N 2 partial pressures and temperatures. NH 3 production is quantified in situ using liquid conductivity measurements coupled with mass spectrometry (MS). Solid-state characterization is performed to identify a surface oxygen layer that necessitates the addition of H 2 during cycling to prevent surface oxidation by trace amounts of O 2 . H 2 concentrations of > 5% H 2 /Ar and temperatures >500 °C are required to reduce Co 3 Mo 3 N to Co 6 Mo 6 N and form NH 3 at 1 bar. Complete regeneration of Co 3 Mo 3 N from Co 6 Mo 6 N is achieved at conditions of 700 °C under 25–75% H 2 /N 2 . H 2 pressure-swings are observed to increase NH 3 production during Co 3 Mo 3 N reduction. In conclusion, the results represent the first comprehensive characterization of and definitive non-catalytic production of NH 3 via chemical looping with metal nitrides and provide insights for technology development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Kinetics of the Carbothermic Reduction of Manganese Oxide from Slag

Experiments were performed using a range of test conditions to elucidate the rate controlling step during the reaction of liquid iron-carbon droplets and slags containing manganese oxide. Four conditions were tested in the system: initial MnO content in the slag (5, 10, and 15 wt pct), initial carbon content of the metal (1, 2.5, 4.3 wt pct), initial droplet mass (0.5, 1.0, and 1.5 g), and reaction temperature (1823 K [1550 °C], 1873 K [1600 °C], and 1923 K [1650 °C]). Data were collected using the Constant Volume Pressure Increase (CVPI) technique which tracked the continuous pressure increase in the sealed furnace over time. Samples were quenched at the end of each experiment and chemistry was checked using LECO Carbon Analysis and ICP (Inductively Coupled Plasma) for manganese. The rate of reaction can be broken into a faster initial period related to internal CO formation, and a slower second reaction controlled by a complex mechanism involving transport of oxygen from slag to metal via CO{sub 2} and decomposition of the CO{sub 2} at the gas–metal interface.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Surface Fe clusters promote syngas reaction to oxygenates on Rh catalysts modified by atomic layer deposition

Converting syngas to higher oxygenates is a promising strategy for sustainably producing fuels and chemicals used every day. Rh-based catalysts promoted with metal oxides have long been of interest for oxygenate synthesis, but the role of promoters and the structure of the catalyst during reaction are often not well understood. In this work, we characterize a Rh/SiO 2 catalyst modified by Fe 2 O 3 deposited by atomic layer deposition (ALD). Here, we show that Fe 2 O 3 deposits selectively on the Rh nanoparticles and enhances both the turnover frequency and the oxygenate selectivity of the catalysts. A maximum 29% selectivity towards higher oxygenates is achieved with just 1 cycle of Fe 2 O 3 ALD, and we relate the trends in selectivity to the changing availability of surface sites that drive higher alcohol (e.g., ethanol and propanol) formation. Further, we show that the ALD promoter mitigates catalyst sintering, improving the stability of these materials. In-situ X-ray absorption spectroscopy experiments reveal that the Fe 2 O 3 undergoes reduction during the catalyst pretreatment and forms Fe clusters on the surface of the Rh that migrate but remain stable under syngas reaction conditions. We find that modification of the Rh with these surface Fe species is key to the enhanced alcohol production observed in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

CO2 Reduction Assembly Prototype Using Microlith-Based Sabatier Reactor for Ground Demonstration

The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) architectures for both low-earth orbit and long-term manned space missions. Carbon dioxide can be reacted with H2, obtained from the electrolysis of water, via Sabatier reaction to produce methane and H2O. Methane can be stored and utilized as propellant while H2O can be either stored or electrolyzed to produce oxygen and regain the hydrogen atoms. Depending on the application, O2 can be used to replenish the atmosphere in human-crewed missions or as an oxidant for robotic and return missions. Precision Combustion, Inc. (PCI), with support from NASA, has previously developed an efficient and compact Sabatier reactor based on its Microlith® catalytic technology and demonstrated the capability to achieve high CO2 conversion and CH4 selectivity (i.e., ≥90% of the thermodynamic equilibrium values) at high space velocities and low operating temperatures. This was made possible through the use of high-heat-transfer and high-surface-area Microlith catalytic substrates. Using this Sabatier reactor, PCI designed, developed, and demonstrated a stand-alone CO2 Reduction Assembly (CRA) test system for ground demonstration and performance validation. The Sabatier reactor was integrated with the necessary balance-of-plant components and controls system, allowing an automated, single "push-button" start-up and shutdown. Additionally, the versatility of the test system prototype was demonstrated by operating it under H2-rich (H2/CO2 of >4), stoichiometric (ratio of 4), and CO2-rich conditions (ratio of <4) without affecting its performance and meeting the equilibrium-predicted water recovery rates. In this paper, the development of the CRA test system for ground demonstration will be discussed. Additionally, the performance results from testing the system at various operating conditions and the results from durability testing will be presented.

Junaedi, Christian↗
DOE OSTI2022

Reflection Optical Imaging to Study Oxygen Evolution Reactions

Discovery of high-efficiency water-splitting catalysts is critical for clean hydrogen fuel generation. Quantitative and reliable chemical imaging methods can play a crucial role in providing critical catalyst efficiency information for materials development and screening. Here, we developed a reflection optical imaging method to map the performance of transition metal oxide catalysts for oxygen evolution reaction (OER). The generated high concentration of oxygen in the electrolyte will decrease the refractive index of the solutions near the electrode and change the reflectivity of optical images. We successfully imaged and measured the OER on cobalt oxide, and the localized current density and overpotential distribution maps have been extracted. The oxidation and reduction of cobalt oxide can be imaged with our reflection optical imaging method as well. These maps showed that the catalytic activities are quite different at different locations, and some regions showed much higher activities. This is due to the non-uniformity created by the catalyst synthesis process and demonstrates the importance of using the optical imaging method to map the localized catalytic efficiency. In addition, the NiFe alloy’s OER catalytic activities have been studied as well. The proposed reflection optical imaging method could find many applications in catalyst activity measurement and screening.

Electrochemistry↗
NASA NTRS2012

Series Bosch System Development

State-of-the-art (SOA) carbon dioxide (CO2) reduction technology for the International Space Station produces methane as a byproduct. This methane is subsequently vented overboard. The associated loss of hydrogen ultimately reduces the mass of oxygen that can be recovered from CO2 in a closed-loop life support system. As an alternative to SOA CO2 reduction technology, NASA is exploring a Series-Bosch system capable of reducing CO2 with hydrogen to form water and solid carbon. This results in 100% theoretical recovery of oxygen from metabolic CO2. In the past, Bosch-based technology did not trade favorably against SOA technology due to a high power demand, low reaction efficiencies, concerns with carbon containment, and large resupply requirements necessary to replace expended catalyst cartridges. An alternative approach to Bosch technology, labeled "Series-Bosch," employs a new system design with optimized multi-stage reactors and a membrane-based separation and recycle capability. Multi-physics modeling of the first stage reactor, along with chemical process modeling of the integrated system, has resulted in a design with potential to trade significantly better than previous Bosch technology. The modeling process and resulting system architecture selection are discussed.

Abney, Morgan B.↗
NASA NTRS2004

Earth's Early Biosphere and the Biogeochemical Carbon Cycle

Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations and weathering. Communities sustained by oxygenic photosynthesis apparently thrived wherever supplies of sunlight, moisture and nutrients were sufficient. Prior to the development of oxygenic photosynthesis, the net global effect of the ancient global biosphere was to facilitate chemical equilibrium between reduced species from thermal activity and weathering and more oxidized constituents in the surface environment. But even this ancient biosphere might have been globally pervasive. The global geothermal heat flow was substantially higher during Earth's first billion years, and thus reduced chemical species might have persisted in sunlit aquatic environments. Perhaps the substantial decline in thermal activity between 4000 and 3000 Ma created a driver for oxygenic photosynthesis to develop.

DesMarais, David↗
DOE OSTI2024

Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts’ functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment. Nanoparticles that exsolve at the surface of the acceptor-type fast-oxygen-ion-conductor SrTi 0.95 Ni 0.05 O 3–δ (STNi) show a high surface mobility leading to a very low thermal stability compared to nanoparticles that exsolve at the surface of donor-type SrTi 0.9 Nb 0.05 Ni 0.05 O 3–δ (STNNi). Our analysis indicates that the low thermal stability of exsolved nanoparticles at the acceptor-doped perovskite surface is linked to a high oxygen vacancy concentration at the nanoparticle-oxide interface. For catalysts that require fast oxygen exchange kinetics, exsolution synthesis routes in dry hydrogen conditions may hence lead to accelerated degradation, while humid reaction conditions may mitigate this failure mechanism.

25 ENERGY STORAGE↗
DOE OSTI2020

CeTi 2 O 6 —A Promising Oxide for Solar Thermochemical Hydrogen Production

A large entropy of reduction is crucial in achieving materials capable of high-efficiency solar thermochemical hydrogen (STCH) production through two-step thermochemical water splitting cycles. We have recently demonstrated that the onsite electronic entropy of reduction attains an extreme value of 4.26 kB at 1500 K in Ce 4+ → Ce 3+ redox reactions, which explains the high performance and uniqueness of CeO 2 as an archetypal STCH material. However, ceria requires high temperatures (T > 1500 °C) to achieve a reasonable reduction extent because of its large reduction enthalpy, which is a major obstacle in practical applications. Therefore, new materials with a large entropy of reduction and lower reduction enthalpy are required. Here, we perform a systematic screening to search for Ce 4+ -based oxides which possess thermodynamics superior to CeO 2 for STCH production. We first search the Inorganic Crystal Structure Database (ICSD) and literature for Ce 4+ -based oxides and subsequently use density functional theory to compute their reduction enthalpies (i.e., oxygen vacancy formation energies). Here, we find that CeTi 2 O 6 with the brannerite structure is the most promising candidate for STCH because it possesses three essential characteristics of an STCH material: (i) a smaller reduction enthalpy compared to ceria yet large enough to split water, (ii) a high thermal stability, as reported experimentally, and (iii) a large entropy of reduction associated with Ce 4+ → Ce 3+ redox. Our proposed design strategy suggests that further exploration of Ce 4+ oxides for STCH production is warranted.

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

NiFe Nanoparticle Nest Supported on Graphene as Electrocatalyst for Highly Efficient Oxygen Evolution Reaction

Abstract Designing cost‐efffective electrocatalysts for the oxygen evolution reaction (OER) holds significant importance in the progression of clean energy generation and efficient energy storage technologies, such as water splitting and rechargeable metal–air batteries. In this work, an OER electrocatalyst is developed using Ni and Fe precursors in combination with different proportions of graphene oxide. The catalyst synthesis involved a rapid reduction process, facilitated by adding sodium borohydride, which successfully formed NiFe nanoparticle nests on graphene support (NiFe NNG). The incorporation of graphene support enhances the catalytic activity, electron transferability, and electrical conductivity of the NiFe‐based catalyst. The NiFe NNG catalyst exhibits outstanding performance, characterized by a low overpotential of 292.3 mV and a Tafel slope of 48 mV dec −1 , achieved at a current density of 10 mA cm − 2 . Moreover, the catalyst exhibits remarkable stability over extended durations. The OER performance of NiFe NNG is on par with that of commercial IrO 2 in alkaline media. Such superb OER catalytic performance can be attributed to the synergistic effect between the NiFe nanoparticle nests and graphene, which arises from their large surface area and outstanding intrinsic catalytic activity. The excellent electrochemical properties of NiFe NNG hold great promise for further applications in energy storage and conversion devices.

Chemistry↗
DOE OSTI2024

Experimental investigation into coal wettability changes caused by reactions with scCO 2 -H 2 O

Geological CO 2 sequestration (GCS) can help mitigate global warming and enhance methane recovery from coal beds. However, few studies have linked the effects of CO 2 to surface chemistry changes controlling wetting behavior in deep coal beds. Contact angles (CAs) of CO 2 /N 2 -high volatile bituminous coal-water systems were measured under different temperatures and pressures. The surface chemistry and physical structure of coals were characterized to investigate changes in physicochemical properties and their relations with wettability after reactions. For N 2 treatment, the time-dependence of static and dynamic CAs were insignificant, ranging within 4°. For gaseous CO 2 treatment, the static CAs and the average advancing angles increased slightly. With supercritical (sc) CO 2 , both the static and dynamic CAs increased significantly, and θ adv changed to intermediate-wet (92°). Reactions with minerals exposed to scCO 2 resulted in greater surface roughness and heterogeneity, greater contact angle hysteresis and more surface sites occupied by scCO 2 rather than H 2 O. Increases in hydrophobic functional groups and decreases in hydrophilicity were shown by FTIR spectra, reflecting the shedding of polar oxygen-containing functional groups, reduction of hydrogen bonds, and increasing percentage of hydrocarbons. XRD patterns obtained following scCO 2 -treatment showed that crystallite growth and molecular polymerization were higher toward graphite-like. The calculated structural parameters of functional groups and crystallites both showed elevated coal rank. Changes in crystallite structure, notably higher carbon content and decreased negative surface charge, are unfavorable for water-wetting. Finally, this study contributes to understanding surface chemistry changes responsible for decreased wettability during CO 2 -enhanced coal bed methane recovery and GCS in coal reservoirs.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Improving the performance for direct electrolysis of CO 2 in solid oxide electrolysis cells with a Sr 1.9 Fe 1.5 Mo 0.5 O 6– δ electrode via infiltration of Pr 6 O 11 nanoparticles

Direct CO 2 electrolysis using solid oxide electrolysis cells (CO 2 -SOECs) holds promise to efficiently convert carbon dioxide to carbon monoxide and oxygen. Cathodes with desirable catalytic activity and chemical stability play a critical role in the development of direct CO 2 -SOECs. Although Sr 2 Fe 1.5 Mo 0.5 O 6–δ (SFM) has exhibited promise for direct CO 2 -SOECs due to its redox stability, it suffers from insufficient activity for the CO 2 reduction reaction (CO 2 RR). Here we report interface engineering of nanosized Pr 6 O 11 on the SFM cathode obtained through infiltration to promote the CO 2 RR performance for direct CO 2 -SOECs. The effect of Pr 6 O 11 loading on the performance of the CO 2 RR is systematically investigated. At 800 °C, the current density of the Pr 6 O 11 infiltrated SFM cathode with an optimum Pr 6 O 11 loading of 14.8 wt% reaches 1.61 A cm –2 at 1.5 V, more than double that of the SFM cathode (0.76 A cm –2 ) under the same operating conditions. X-ray photoelectron spectroscopy (XPS) characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicate that the adsorption ability of CO 2 on the SFM cathode has been significantly improved by the formation of Pr 6 O 11 . Temperature-programmed desorption (TPD) of CO 2 measurements further manifest that a 14.8 wt% Pr 6 O 11 -SFM cathode has better CO desorption capacity. In addition, polarization resistance of the SFM cathode has significantly decreased with the addition of Pr 6 O 11 . Three-electrode measurement was used to analyze the improved electrode kinetics. Finally, these results demonstrate that the formation of Pr 6 O 11 in the SFM cathode through infiltration is a promising approach for increasing CO 2 RR activity for CO 2 -SOECs.

03 NATURAL GAS↗
NASA NTRS2006

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Mittlefehldt, D. W.↗
DOE OSTI2020

Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron-Proton Transfer Mediators

CONSPECTUS: Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron-proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radical-cation intermediates by supporting mechanisms that operate at electrode potentials much lower (=1 V) than analogous direct electrolysis reactions. The stable aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl) is an effective mediator for electrochemical alcohol oxidation, and we have employed such processes for applications ranging from pharmaceutical synthesis to biomass conversion. A complementary electrochemical alcohol oxidation method employs a cooperative Cu/TEMPO mediator system that operates at 0.5 V lower electrode potential than the TEMPO-only mediated process. This difference, which arises from a different catalytic mechanism, rationalizes the broad functional group tolerance of Cu/TEMPO-based aerobic alcohol oxidation catalysts. Aminoxyl mediators address long-standing challenges in the "Shono oxidation", an important method for a-C–H oxidation of tertiary amides and carbamates. Shono oxidations are initiated by a high-potential SET step that limits their utility. Aminoxyl-mediated Shono-type oxidations have been developed that operate at much lower potentials and tolerate diverse functional groups. Analogous reactivity underlies a-C–H cyanation of secondary cyclic amines, a new method that enables efficient diversification of piperidine-based pharmaceutical building blocks and preparation of non-natural amino acids. Electrochemical oxidations of benzylic C–H bonds are commonly initiated by SET to generate radical cations, but such methods are again plagued by large overpotentials. Mediated electrolysis methods that promote hydrogen-atom-transfer (HAT) from benzylic C–H bonds to Fe-oxo species and phthalimide N-oxyl (PINO) support C–H oxygenation, iodination, and oxidative-coupling reactions. A complementary method merges photochemistry with electrochemistry to achieve amidation of C(sp3)–H bonds. This unique process operates at much lower overpotentials compatible with diverse functional groups. These results have broad implications for organic electrochemistry, highlighting the importance of "overpotential" considerations and the prospects for expanding synthetic utility by using mediators to bypass high-energy outer-sphere electron-transfer mechanisms. Principles demonstrated here for oxidation are equally relevant to electrochemical reductions.

Wang, Fei↗
DOE OSTI2026

Tandem bulk oxygen diffusion and surface reactions in reducible metal oxides control redox cycle dynamics

The interplay between bulk oxygen diffusion and surface reactions in reducible metal oxides is key in heterogeneous catalysts, but direct measurements of oxygen mobility, transient kinetics, and in situ spectroscopies have been lacking. Here, we reveal complex dynamic behavior of ceria-zirconia by H 2 using transient kinetics via mass spectrometry and in situ Raman and near-ambient pressure x-ray photoelectron spectroscopies. Molecular dynamics simulations with a machine learning potential delineate competitive oxygen diffusion mechanisms, with an optimal mobility at intermediate reductions. We expose a compensation between vacancy availability and lattice distortion at intermediate to high reductions and Frenkel defects at low reductions, underscoring a potential deficiency of 16 O/ 18 O exchange experiments in deducing oxygen mobility. Vacancies in proximity require electron localization on Ce atoms further away. The continuous replenishment of surface oxygen results in a varying reduction rate, with H 2 dissociation being the rate-limiting step. Multiscale transient simulations, consistent with experiments, indicate catalysts of potentially spatially varying oxidation states. The approach is broadly applicable to reducible oxide materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Spin‐Polarized Interfaces Redirect CO 2 Reduction From CO to Formate

Achieving high product selectivity in electrocatalytic carbon dioxide reduction (CO 2 RR) remains a critical challenge due to competition between multiple proton-coupled electron-transfer pathways on catalyst surfaces. Meanwhile, chirality-induced spin selectivity (CISS), which enables spin-polarized electron transport through chiral interfaces, has recently emerged as a promising strategy to modulate interfacial electrochemical reactions. Although the CISS effect has been shown to enhance selectivity and efficiency in the spin-sensitive oxygen evolution reaction (OER), its role in regulating CO 2 RR pathways and in stabilizing intermediates remains largely unexplored. Here, chiral molecules (R- and S-1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, BNP) were integrated with SnO 2 to construct chiral-modified catalysts (R-BNP/SnO 2 and S-BNP/SnO 2 ). Compared with bare SnO 2 and racemic BNP-modified SnO 2 (Rac-BNP/SnO 2 ), the chiral catalysts exhibited a pronounced shift in product selectivity from CO toward formate production. Importantly, in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals that the chiral interface selectively stabilizes the O-bound *OCHO intermediate associated with the formate pathway and modulates interfacial water structure and hydrogen-bonding dynamics. These findings demonstrate that spin-polarized interfacial electron transfer can regulate CO 2 RR pathway selectivity by modulating the stabilization of key intermediates. More broadly, this work establishes chiral spin-selective interfaces as a new strategy for regulating competitive electrocatalytic reaction pathways.

14 SOLAR ENERGY↗
DOE OSTI2024

Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H 2 followed by O 2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate determining. Electronic structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from that involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H 2 and, alternatively, with D 2 on the cluster incorporating the dioxygen ligands, and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H 2 with D 2 to give HD. Here, we posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

02 PETROLEUM↗