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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 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

PCET‐Driven Reactivity of Neptunyl(VI) Yields Oxo‐Bridged Np(V) and Np(IV) Species

Two unconventional polynuclear complexes of neptunium (Np) featuring mono-mathematical equation -oxo motifs have been accessed by proton-coupled electron transfer (PCET) reactivity involving the dissolution of neptunyl(VI) diacetate dihydrate (NpO 2 (OAc) 2 (H 2 O) 2 ∙ HOAc) in methanol followed by addition of a pentadentate Schiff-base ligand. One complex is a mixed-valent [Np V ,Np IV , Np V ] trimer with two bridging mathematical equation μ 2 -oxos and the other is a [Np V , Np V ] dimer featuring a single mathematical equation μ 2 -oxo. In both complexes the outer Np centers are capped with terminal oxo ligands. Spectroscopic and spectrokinetic studies aimed at elucidating mechanistic details of complex formation in this system show that intermediate multinuclear [Np V O 2 (OAc)] n species form prior to metal chelation by the ligand; electrolysis experiments demonstrate that production of Np(V) gives rise to asynchronous proton transfer that does not occur otherwise (in the Np(VI) state) as well as condensation with loss of H 2 O and formation of the polynuclear complexes. We attribute the oxo-deficient nature of these products, with respect to conventional actinyl ([AnO 2 ] m+ ) species, to the reduction/condensation reaction sequence of PCET.

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

Emergent Constrained Projections of Mean and Extreme Warming in China

Reliable regional temperature projections including heat extremes are essential for climate change adaptation and mitigation. Taking China as an example, simple averages from Coupled Model Intercomparison Project Phase 6 (CMIP6) models project high warming due to sampling many high climate sensitivities in the ensemble. Here, we develop an emergent constraint (EC) framework to obtain constrained mean and daily maximum temperature (TXx) warming over China by using observed global warming and local residual warming. The constrained annual mean and TXx warming over China (2.33°C [1.61–3.05°C] and 2.31°C [1.21–2.99°C]) are 0.65°C [0.04–1.76°C] and 0.63°C [–0.50–2.39°C], respectively, lower than raw projections (2.98°C [1.85–4.22°C] and 2.94°C [2.04–4.39°C]) for 2080–2099 under the intermediate-emission scenario. Approximately half model uncertainty is reduced after constraint. The land area (population) experiencing temperature extremes in our metric is 78% (85%) of the raw projections. Our results imply a lower impact of extreme heat than implied by current raw CMIP6 projections.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

KEPLER-68: THREE PLANETS, ONE WITH A DENSITY BETWEEN THAT OF EARTH AND ICE GIANTS

NASA's Kepler Mission has revealed two transiting planets orbiting Kepler-68. Follow-up Doppler measurements have established the mass of the innermost planet and revealed a third Jovian-mass planet orbiting beyond the two transiting planets. Kepler-68b, in a 5.4 day orbit, has M{sub P}=8.3{sup +2.2}{sub -2.4} M{sub Circled-Plus }, R{sub P}=2.31{sup +0.06}{sub -0.09} R{sub Circled-Plus }, and {rho}{sub P}=3.32{sup +0.86}{sub -0.98} g cm{sup -3}, giving Kepler-68b a density intermediate between that of the ice giants and Earth. Kepler-68c is Earth-sized, with a radius R{sub P}=0.953{sup +0.037}{sub -0.042} R{sub Circled-Plus} and transits on a 9.6 day orbit; validation of Kepler-68c posed unique challenges. Kepler-68d has an orbital period of 580 {+-} 15 days and a minimum mass of M{sub P}sin i = 0.947 {+-} 0.035M{sub J} . Power spectra of the Kepler photometry at one minute cadence exhibit a rich and strong set of asteroseismic pulsation modes enabling detailed analysis of the stellar interior. Spectroscopy of the star coupled with asteroseismic modeling of the multiple pulsation modes yield precise measurements of stellar properties, notably T{sub eff} = 5793 {+-} 74 K, M{sub *} = 1.079 {+-} 0.051 M{sub Sun }, R{sub *} = 1.243 {+-} 0.019 R{sub Sun }, and {rho}{sub *} = 0.7903 {+-} 0.0054 g cm{sup -3}, all measured with fractional uncertainties of only a few percent. Models of Kepler-68b suggest that it is likely composed of rock and water, or has a H and He envelope to yield its density {approx}3 g cm{sup -3}.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2001

Rapid flow-induced responses in endothelial cells

Endothelial cells alter their morphology, growth rate, and metabolism in response to fluid shear stress. To study rapid flow-induced responses in the 3D endothelial cell morphology and calcium distribution, coupled fluorescence microscopy with optical sectioning, digital imaging, and numerical deconvolution techniques have been utilized. Results demonstrate that within the first minutes of flow application nuclear calcium is increasing. In the same time frame whole cell height and nuclear height are reduced by about 1 microm. Whole cell height changes may facilitate reduction of shear stress gradients on the luminal surface, whereas nuclear structural changes may be important for modulating endothelial growth rate and metabolism. To study the role of the cytoskeleton in these responses, endothelial cells have been treated with specific disrupters (acrylamide, cytochalasin D, and colchicine) of each of the cytoskeleton elements (intermediate filaments, microfilaments, and microtubules, respectively). None of these compounds had any effect on the shear-induced calcium response. Cytochalasin D and acrylamide did not affect the shear-induced nuclear morphology changes. Colchicine, however, completely abrogated the response, indicating that microtubules may be implicated in force transmission from the plasma membrane to the nucleus. A pedagogical model based on tensegrity theory principles is presented that is consistent with the results on the 3D endothelial morphology.

Non-NASA Center↗
DOE OSTI2023

Emerging concepts in intermediate carbon dioxide emplacement to support carbon dioxide removal

Substantial upscaling of carbon dioxide capture is possible in the coming decades but existing solutions for storage are projected to be limited in annual capacity by as much as 2–10 GtCO 2 per year until mid-century. Temporary storage of CO 2 in a solid or liquid state could prove useful for filling this gap in capacity, until more permanent and ideally lucrative CO 2 sequestration options come online. There are several concepts for reversible solid-state and chemical CO 2 storage, but their advantages and limitations have yet to be reviewed in this context. This article focuses on the physical and chemical aspects of CO 2 storage via liquid and solid chemical carriers and sorbents, and gives an overview of the energetics around their use, as well as prospects for their future development. Exciting opportunities for coupling capture and medium to high maturity multi-year storage technologies could support carbon removal in the coming decades. Highlights of the analysis are the remarkable storage capacity of oxalic acid and formic acid (CO 2 -density of 1857 kg m –3 and 1152 kg m –3 , compared with condensed liquid CO 2 at 993–1096 kg m –3 , respectively), the relative scalability and compatibility of carbonate salts for stationary storage with direct air capture, and the potential promise of multiple carriers for CO 2 transportation. Solid sorbents do not achieve such ultra-high storage capacities, but could improve storage over compressed gas tanks on a capacity and energetics basis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

Theory of two-dimensional self-assembly of Janus colloids: crystallization and orientational ordering

We study the rich crystalline phase behavior of amphiphilic spherical Janus colloids using a new formulation of self-consistent phonon theory that includes coupled translational and rotational entropic and enthalpic contributions to the free energy. In contrast to homogeneous spheres, broken rotational symmetry can result in more exotic crystals that possess distinct orientational patterns, and also plastic crystals. Ground states are identified based on the compatibility between the patch geometry of particles (e.g., patch coverage, number, shape) and lattice symmetry. We derive the explicit coupled self-consistent equations for translational and rotational localization parameters for effectively 2-dimensional dense monolayers of Janus crystals. The equations are numerically solved for a given crystal symmetry, thermodynamic state, and patch orientational order, and the thermodynamic stability of different phases is determined. For hexagonal packing, we predict with increasing temperature or decreasing attraction strength the possibility of a phase sequence of maximally bonded zigzag stripe, trimer, and rotationally disordered plastic crystal phases (or a phase sequence of trimer, dimer, and plastic crystal), which depends sensitively on particle chemical composition (Janus balance) and pressure. Here, the role of rotational entropy in stabilizing the intermediate trimer (or dimer) phase at intermediate temperatures and high pressures is discussed in detail. Evolution of the center-of-mass vibrational and rotational amplitudes with thermodynamic state and Janus balance is also determined.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Fractional quantum Hall bilayers at half filling: Tunneling-driven non-Abelian phase

Multicomponent quantum Hall systems with internal degrees of freedom provide a fertile ground for the emergence of exotic quantum liquids. Here, we investigate the possibility of non-Abelian topological order in the half-filled fractional quantum Hall (FQH) bilayer system driven by the tunneling effect between two layers. By means of the state-of-the-art density-matrix renormalization group, we unveil “fingerprint” evidence of the non-Abelian Moore-Read Pfaffian state emerging in the intermediate-tunneling regime, including the ground-state degeneracy on the torus geometry and the topological entanglement spectroscopy (entanglement spectrum and topological entanglement entropy) on the spherical geometry, respectively. Remarkably, the phase transition from the previously identified Abelian (331) Halperin state to the non-Abelian Moore-Read Pfaffian state is determined to be continuous, which is signaled by the continuous evolution of the universal part of the entanglement spectrum, and discontinuities in the excitation gap and the derivative of the ground-state energy. Our results not only provide a “proof-of-principle” demonstration of realizing a non-Abelian state through coupling different degrees of freedom, but also open up a possibility in FQH bilayer systems for detecting different chiral p-wave pairing states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol

Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (H 2 SO 4 ) are well-known natural precursors of atmospheric aerosols, contributing to particle mass and cloud formation over ocean and coastal regions. Despite a long recognized and well-studied role in the marine troposphere, DMS oxidation chemistry remains a work in progress within many current air quality and climate models, with recent advances exploring heterogeneous chemistry and uncovering previously unknown intermediate species. With the identification of additional DMS oxidation path ways and intermediate species that influence the eventual fate of DMS, it is important to understand the impact of these pathways on the overall sulfate aerosol budget and aerosol size distribution. In this work, we update and evaluate the DMS oxidation mechanism of the chemical transport model GEOS-Chem by implementing expanded DMS oxidation pathways in the model. These updates include gas- and aqueous-phase reactions, the formation of the intermediates dimethyl sulfoxide (DMSO) and methanesulfinic acid (MSIA), and cloud loss and aerosol uptake of the recently quantified intermediate hydroperoxymethyl thioformate (HPMTF). We find that this updated mechanism collectively decreases the global mean surface-layer gas-phase sulfur dioxide (SO 2 ) mixing ratio by 40 % and enhances the sulfate aerosol ($SO^{2-}_{4}$) mixing ratio by 17 %. We further perform sensitivity analyses exploring the contribution of cloud loss and aerosol uptake of HPMTF to the overall sulfur budget. Comparing modeled concentrations to available observations, we find improved biases relative to previous studies. To quantify the impacts of these chemistry updates on global particle size distributions and the mass concentration, we use the TwO-Moment Aerosol Sectional (TOMAS) aerosol microphysics module coupled to GEOS-Chem and find that changes in particle formation and growth affect the size distribution of aerosol. With this new DMS-oxidation scheme, the global annual mean surface-layer number concentration of particles with diameters smaller than 80 nm decreases by 16.8 %, with cloud loss processes related to HPMTF being mostly responsible for this reduction. However, the global annual mean number of particles larger than 80 nm (corresponding to particles capable of acting as cloud condensation nuclei, CCN) increases by 3.8 %, suggesting that the new scheme promotes seasonal particle growth to these sizes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Gravitational waves from an inflation triggered first-order phase transition

Large excursion of the inflaton field can trigger interesting dynamics. One important example is a first-order phase transition in a spectator sector which couples to the inflaton. Gravitational waves (GWs) from such a first-order phase transition during inflation, an example of an instantaneous source, have an oscillatory feature. In this work, we show that this feature is generic for a source in an era of accelerated expansion. We also demonstrate that the shape of the GW signal contains information about the evolution of the early universe following the phase transition. In particular, the slope of the infrared part of the GW spectrum is sensitive to the evolution of the Hubble parameter when the GW modes reenter the horizon after inflation. The slope of the profile of the intermediate oscillatory part and the ultraviolet part of the GW spectrum depend on the evolution of the Hubble parameter when the modes exit horizon during the inflation and when they reenter the horizon during the reheating. The ultraviolet spectrum also depends on the details of the dynamics of the phase transition. We consider the GW signal in several models of evolution during and after inflation, and compare them with the minimal scenario of quasi- de Sitter inflation followed by radiation domination after a fast reheating, and demonstrate that the shape of the GW can be used to distinguish them. In this way, the GW signal considered in this paper offers a powerful probe to the dynamics of the early universe which is otherwise difficult to explore directly through CMB, large scale structure, big bang nucleosynthesis (BBN), and other well-studied cosmological observables.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Data for secondary-electron production from ion precipitation at Jupiter II: Simultaneous and non-simultaneous target and projectile processes in collisions of O{sup q+} + H{sub 2} (q=0–8)

To improve the physical completeness of the data previously calculated (Schultz et al., 2017) to enable modeling of the effects of secondary electrons produced by energetic ion precipitation at Jupiter, we extend the treatment to include inelastic processes that occur simultaneously on the projectile (O{sup q+}, q=0–8)) and target (H{sub 2}). Here, processes considered in the previous work (single and double ionization, transfer ionization, double capture with subsequent autoionization, single and double stripping, single and double charge transfer, and target excitation) reflecting non-simultaneous projectile and target electron transitions, are replaced with processes that include both non-simultaneous and simultaneous electronic transitions on the target and projectile. These include, for example, single ionization, single ionization with simultaneous single projectile excitation, single ionization with double projectile excitation, single ionization with single projectile stripping, and single ionization with double projectile stripping. Using this expanded set of processes, we show, via Monte Carlo ion-transport simulation, that improved representation of the energy deposition, measured by the stopping power, is obtained as compared to accepted recommended values for intermediate energies (100–2000 keV/u) where the stopping power is largest, while maintaining the existing good agreement with these recommended values for low (∼10–100 keV/u) and high (≥2000 keV/u) energies. In addition, the ion-fraction distribution is altered by use of the improved data set. Both of these effects have implications for the energy deposition by oxygen ion precipitation in an H{sub 2} atmosphere. Therefore, use of this expanded data set can provide a more physically realistic secondary-electron distribution, and consequently improved atmospheric reaction network, improved description of ion contribution to atmospheric currents, and therefore improved understanding of Jovian ionosphere–atmosphere coupling.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Pulsating one-dimensional detonation in ammonia-hydrogen–air mixtures

In this study, one-dimensional detonations in ammonia/hydrogen-air mixtures are numerically investigated by solving the fully compressible Navier-Stokes equations with detailed chemistry. Pulsating instabilities with single-mode are observed during the detonation wave propagation, accompanied by periodic coupling and decoupling of the lead shock wave and the reactive front. The ratio between driver pressure and initial pressure determines the overdrive degree and thus the oscillatory mode of detonation for a premixture with certain composition. The effects of hydrogen dilution and mixture equivalence ratio on pulsating detonations are also examined under a constant driver pressure. The growing hydrogen fraction in fuel blends significantly increases the oscillation frequency. In addition, the pulsating detonation frequency rises with increasing equivalence ratio under fuel-lean conditions, peaks under stoichiometric conditions, and falls under fuel-rich conditions as the equivalence ratio increases further. Evolutions of reactants, main intermediate radicals, and products are analysed in both fuel-lean and fuel-rich conditions. A chemical explosive mode analysis further confirms the highly-autoignitive nature of the mixture in the induction zone between reaction front and shock front where thermal diffusion plays a negligible role.

08 HYDROGEN↗
DOE OSTI2015

Ionization competition effects on population distribution and radiative opacity of mixture plasmas

Ionization competition arising from the electronic shell structures of various atomic species in the mixture plasmas was investigated, taking SiO{sub 2} as an example. Using a detailed-level-accounting approximation, we studied the competition effects on the charge state population distribution and spectrally resolved and Planck and Rosseland mean radiative opacities of mixture plasmas. A set of coupled equations for ionization equilibria that include all components of the mixture plasmas are solved to determine the population distributions. For a given plasma density, competition effects are found at three distinct temperature ranges, corresponding to the ionization of M-, L-, and K-shell electrons of Si. Taking the effects into account, the spectrally resolved and Planck and Rosseland mean opacities are systematically investigated over a wide range of plasma densities and temperatures. For a given mass density, the Rosseland mean decreases monotonically with plasma temperature, whereas Planck mean does not. Although the overall trend is a decrease, the Planck mean increases over a finite intermediate temperature regime. A comparison with the available experimental and theoretical results is made.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Lessons from the IEC Durability of Adhesion Accelerated Test Sequence

The IEC 62788-1-1 and IEC 63209-2 standards use aging sequences for durability of adhesion in photovoltaic (PV) modules, which may be evaluated using the single cantilever beam (SCB) test. Because the encapsulant forms critical interfaces with the front glass and solar cells, degradation at those interfaces under ultraviolet (UV) exposure, elevated temperature, and humidity can lead to interfacial delamination - compromising the long-term reliability. In this work, adhesion durability of UV-transmitting poly(ethylene-co-vinyl acetate) (EVA) encapsulant to glass and to silicon solar cells is evaluated after sequenced UV and damp heat aging (85C/85%RH). Laminates were prepared using StarPhire solar front glass with thin glass or PERC cells, and two EVA formulations with different concentrations of siloxane coupling agent. Adhesion was quantified by measuring critical debond energy using the SCB method. Both formulations exhibit similar qualitative trends, while different adhesion is observed at the periphery despite the use of low-shrink manufacturing. The results show that while glass/EVA adhesion remains stable or increases after UV exposure and shows only moderate changes after damp heat, the EVA/cell interface exhibits an irreversible loss of adhesion following UV and then damp heat exposure. Although glass/EVA interfaces generally exhibit lower debond energies, the EVA/cell interface is significantly more vulnerable to UV-driven degradation, identifying it as the dominant reliability risk location through early- and intermediate-module life. These results demonstrate that accelerated aging sequences can expose large, interface-specific losses in adhesion durability and underscore the importance of interface engineering for long-term PV module reliability.

14 SOLAR ENERGY↗
NASA NTRS2022

Space Weather Modeling and Prediction for Intermediate Time-scales

Much of solar activity within a sunspot cycle occurs as bursts, or 'seasons' of strong activity over several months, separated by periods of much less activity. The most important space weather effects occur during these bursts. Previous modeling and forecasting efforts have focused on time-scales of hours-to-days and decades-to-centuries. The recent discovery of Rossby waves in the Sun, together with recently developed global models of solar MHD Rossby waves and their interactions with differential rotation and spot-producing magnetic fields, reveal the opportunity to simulate and predict the occurrence, strength and location of enhanced activity bursts a few weeks up to several months in advance. We now have a golden opportunity to fill in this gap in time-scales of forecasting space weather. This requires a) continuous observations of solar Rossby waves by various techniques; b) development of coupled nonlinear MHD models that simulate both global Rossby waves and the much smaller spatial scale emergence of new active regions; c) application of advanced data assimilation techniques to couple surface observations to update the model-system to integrate forward in time for creating forecasts months ahead. Then it will be possible to build operational prediction models to meet the needs of customers and stakeholders, including support of future NASA missions, regarding what kind and level of space weather to expect a few weeks to several months ahead.

SMD↗
DOE OSTI2010

Direct evidence of three-body interactions in a cold {sup 85}Rb Rydberg gas

Cold Rydberg atoms trapped in a magneto-optical trap (MOT) are not isolated and they interact through dipole-dipole and multipole-multipole interactions. First-order dipole-dipole interactions and van der Waals interactions between two atoms have been intensively studied. However, the facts that the first-order dipole-dipole interactions and van der Waals interactions show the same size of broadening [A. Reinhard, K. C. Younge, T. C. Liebisch, B. Knuffman, P. R. Berman, and G. Raithel, Phys. Rev. Lett. 100, 233201 (2008)] and there are transitions between two dimer states [S. M. Farooqi, D. Tong, S. Krishnan, J. Stanojevic, Y. P. Zhang, J. R. Ensher, A. S. Estrin, C. Boisseau, R. Cote, E. E. Eyler, and P. L. Gould, Phys. Rev. Lett. 91, 183002 (2003); K. R. Overstreet, Arne Schwettmann, Jonathan Tallant, and James P. Shaffer, Phys. Rev. A 76, 011403(R) (2007)] cannot be explained by the two-atom picture. The purpose of this article is to show the few-body nature of a dense cold Rydberg gas by studying the molecular-state microwave spectra. Specifically, three-body energy levels have been calculated. Moreover, the transition from three-body energy levels to two-body coupled molecular energy levels and to isolated atomic energy levels as a function of the internuclear spacing is studied. Finally, single-body, two-body, and three-body interaction regions are estimated according to the experimental data. The results reported here provides useful information for plasma formation, further cooling, and superfluid formation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Colloidal Synthesis of Palladium Nanocluster‐Decorated Cs 3 Sb 2 Cl 9 Perovskite Heterostructural Nanorods for Enhanced CO 2 Photoreduction

Developing efficient and sustainable photocatalysts for CO 2 reduction remains a significant challenge, particularly with environmentally benign materials. Here, in this study, we report the first one-step synthesis of metal–lead-free perovskite heterostructural nanocrystals by decorating Cs 3 Sb 2 Cl 9 perovskite nanorods with size-controlled Pd nanoclusters via a one-step hot-injection method. The resulting Pd-Cs 3 Sb 2 Cl 9 heteronanorods (HNRs) exhibit strong interfacial electronic coupling, enhanced charge separation, and excellent colloidal stability. Transient absorption spectroscopy and DFT calculations reveal a built-in electric field that drives directional electron transfer from the perovskite host to the Pd domains. Under UV irradiation, the Pd-Cs 3 Sb 2 Cl 9 HNRs demonstrate excellent CO 2 photoreduction activity with high CH 4 selectivity, achieving a record apparent quantum yield (AQY) of 2.62% among halide perovskite nanocrystal-based systems with a large electronic yield of 689.3 ± 12.2 µmol·g cat −1 . In situ spectroscopic monitoring and Gibbs free energy analysis further unveil a Pd-facilitated reaction pathway involving stabilization of key intermediates. This work introduces a new class of lead-free perovskite-based heterostructures through a facile one-step synthesis strategy and offers a new design principle for next-generation photocatalysts for solar fuel production.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Mechanistic Insights into Dinitrogen Reduction to Ammonia in Light-Controlled Nanocrystal:Nitrogenase Complexes

Developing systems that can efficiently capture photon energy and convert this energy into fuels and chemicals requires understanding how to assemble molecular components with diverse functions into complete systems possessing selectivity and efficiency in directing charge carriers to catalytic reactions. There are many challenges to achieving this goal. One promising approach is the development of hybrid systems that combine semiconductor nanocrystals (NCs) for light capture and enzymes as efficient catalysts. Such biohybrid systems capitalize on the tunable electronic and optical properties of NCs while leveraging the unmatched specificity and efficiency of enzymes in catalyzing chemical reactions, thereby offering opportunities to surpass the limitations of each component alone. Here, we focus on recent progress in developing a biohybrid system that combines CdS NCs for photon capture with the enzyme nitrogenase to accomplish light-driven dinitrogen (N 2 ) reduction to ammonia (NH 3 ). Integrating light-harvesting materials with biological catalysts requires a deep understanding of NC properties, protein stability, and electron transfer (ET), making it an inherently multidisciplinary problem. The reduction of N 2 to NH 3 is a challenging reaction, with a high demand in both agriculture and industrial chemical production. This reaction is intrinsically energy intensive, due to the need to activate the N≡N triple bond. The current standard industrial approach to N 2 reduction, the Haber−Bosch reaction, obtains the necessary energy input from fossil fuels, whereas biological systems capable of N 2 reduction utilize the hydrolysis of ATP as their energy source. Replacing these costly, energy-intensive inputs with renewable light energy represents a critical step toward sustainable NH 3 production. Recent progress has demonstrated that semiconductor CdS NCs can be coupled to the catalytic component of nitrogenase, the MoFe protein, to form a biohybrid CdS NC:MoFe protein complex, enabling light-driven N 2 reduction rather than energy input from fossil fuels or ATP. This illustrates how inorganic NCs can functionally replace the natural Fe protein partner, yielding a biohybrid catalyst that enables controlled electron delivery and provides not only light-driven NH 3 production but also new approaches for probing enzyme catalytic function. The CdS NC:MoFe protein biohybrid system enables light-initiated electron delivery at ambient temperature, as well as temperatures below freezing, allowing for stabilization and spectroscopic characterization of key reaction intermediates. These findings highlight how photochemical biohybrids can serve as both functional catalysts and mechanistic probes. Beyond studies of the nitrogenase mechanism, studies of the CdS NC:MoFe system reveal how variables such as NC size, electrostatic binding interactions, and sacrificial electron donors (SEDs) govern complex stability, charge transfer efficiency, and catalytic performance. In addition, studies of nitrogenase and the high activation barrier for N 2 reduction are enabling investigations of new and interesting questions regarding the properties and limitations of NC biocatalysis. In this Account, we describe the key features of CdS NC:MoFe protein biohybrids and the parameters for optimal light-driven N 2 reduction, and how controlling ET with light illuminates the path to new insights into the nitrogenase mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗