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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Towards Energy–Efficient Direct Air Capture with Photochemically–Driven CO 2 Release and Solvent Regeneration

The intensive energy demands associated with solvent regeneration and CO 2 release in current direct air capture (DAC) technologies makes their deployment at the massive scales (GtCO 2 /year) required to positively impact the climate economically unfeasible. This challenge underscores the critical need to develop new DAC processes with significantly reduced energy costs. Recently, we developed a new approach to photochemically drive efficient release of CO 2 through an intermolecular proton transfer reaction by exploiting the unique properties of an indazole metastable-state photoacid (mPAH), opening a new avenue towards energy efficient on-demand CO 2 release and solvent regeneration using abundant solar energy instead of heat. In this Concept Article, we will describe the principle of our photochemically-driven CO 2 release approach for solvent-based DAC systems, discuss the essential prerequisites and conditions to realize this cyclable CO 2 release chemistry under ambient conditions. We outline the key findings of our approach, discuss the latest developments from other research laboratories, detail approaches used to monitor DAC systems in situ, and highlight experimental procedures for validating its feasibility. Finally, we conclude with a summary and outlook into the immediate challenges that must be addressed in order to fully exploit this novel photochemically-driven approach to DAC solvent regeneration.

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

Regulatory Coordination of Photophysical, Photochemical, and Biochemical Reactions in the Photosynthesis of Land Plants

Balance among the sequential photophysical, photochemical, and biochemical reactions of photosynthesis is needed for converting fleeting energy in light to stable energy in chemical bonds. Any imbalance acts as either a bottleneck for limiting photosynthetic efficiency or an agent for inducing structural and functional damage to photosynthetic apparatus. Not only must each reaction be carefully regulated, but regulatory processes must also be coordinated across the reactions. However, regulations of different stages of photosynthesis have rarely been studied jointly. Non-photochemical quenching (NPQ) and stomatal conductance (g s ) are key regulators of photophysical and biochemical reactions, respectively. Existing evidence suggests that the redox state of plastoquinone regulates g s and that the photochemical reactions are partially regulated by the ultrastructural dynamics of thylakoids induced by osmotic water fluxes in chloroplasts of land plants. To examine how these regulations are coordinated and feedback to each other, we simultaneously measured NPQ and gs and inferred the redox state of plastoquinone and the light-induced thylakoid swelling/shrinking on numerous C 3 and C 4 species. For all species measured, NPQ and gs covary with the redox states of the electron transport chain, particularly plastoquinone, and increase as thylakoid swelling is inferred. NPQ has the maximal sensitivity at the light intensity at which thylakoid is inferred to be fully swollen. Our findings suggest that plant energy and water use strategies are intimately linked by evolution, and studying the regulations of different photosynthetic stages as a whole can lead to new insights of the functioning of photosynthetic machinery in dynamic environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Photochemical CO 2 Reduction by a Postsynthetically Modified Zr-MOF

Metal–organic frameworks are an excellent platform for photochemical CO 2 reduction into valuable chemicals. Herein, we report the synthesis and photocatalytic behavior of Ru@MOF-808, a Zr-based MOF, modified with a Ru-polypyridyl complex. The postsynthetic modification was achieved using solvent-assisted incorporation of bipyridine–carboxylate ligands onto the nodes of the MOF-808, followed by the coordination of Ru­(II)-terpyridine moiety. A thorough characterization including 1 H NMR, diffuse reflectance UV/vis, X-ray absorption spectroscopy and gas adsorption studies, combined with DFT calculations, provides strong support for efficient incorporation of the molecular Ru-complex at the loading of one Ru center per node. In the presence of a strong sacrificial reductant BIH, Ru@MOF-808 was found to catalyze the photochemical reduction of CO 2 into a mixture of CO and formate ion. When compared to the homogeneous model catalyst Ru­(tpy)­(bpy) 2+ , Ru@MOF-808 was found to exhibit higher formate yields. Additionally, to explain these formate enhancements, we propose a mechanism that involves CO 2 capture at the MOF nodes to form Zr-bicarbonate species, which further react in a hydride transfer reaction with photogenerated Ru–H donor, thereby outperforming molecular catalysts in HCOO – production. Overall, the results presented in this work indicate the potential of Zr-based MOFs in integrating CO 2 capture with its photochemical conversion to desired products.

CO2 reduction↗
DOE OSTI2022

Toward Metal-free Photocatalysis: Photochemical Regeneration of Organic Hydride Donors Using Phenazine-Based Photosensitizers

Earth-abundant chromophores and catalysts are important molecular building blocks for artificial photosynthesis applications. Our team previously reported that metal-free hydride donors, such as biomimetic benzoimidazole-based motifs, can reduce CO 2 selectively to the formate ion and that they can be electrochemically regenerated using the proton-coupled mechanism. To enable direct utilization of solar energy, we report here the photochemical regeneration of a benzoimidazole-based hydride donor using a phenazine-based metal-free chromophore. The photochemical regeneration was investigated under different experimental conditions involving varying sacrificial donors, proton donors, solvents, and component concentrations. The best hydride regeneration yield of 50% was obtained with phenol as a proton source and thiophenolate as a sacrificial electron donor. The mechanism of photochemical regeneration was studied using steady-state and time-resolved UV/Vis spectroscopies. Based on the results of these studies, we hypothesize that the initial photoinduced electron transfer from photoexcited phenazine chromophores involves the benzoimidazole cation and that this process is likely coupled with proton transfer to generate protonated benzoimidazole-based radical cation. The second photoinduced electron transfer is hypothesized to generate the hydride form. Furthermore, our findings provide the requisite information for the future development of reductive photocatalysts for solar energy and light-harvesting applications utilizing earth-abundant metal-free materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Defining Intermediates of Nitrogenase MoFe Protein during N 2 Reduction under Photochemical Electron Delivery from CdS Quantum Dots

Coupling the nitrogenase MoFe protein to light-harvesting semiconductor nanomaterials replaces the natural electron transfer complex with Fe protein and ATP and provides low potential photoexcited electrons for photocatalytic N 2 reduction. A central question is how direct photochemical electron delivery from nanocrystals to MoFe protein is able to support the multi-electron ammonia production reaction. In this study, low photon flux conditions were used to identify the initial reaction intermediates of CdS quantum dot (QD):MoFe protein nitrogenase complexes under photochemical activation. Illumination of CdS QD:MoFe protein complexes led to redox changes in the MoFe protein active site FeMo-co observed as the gradual decline in E0 resting state intensity that was accompanied by an increase in intensity of a new “g eff = 4.5” EPR signal. The magnetic properties of the g eff = 4.5 signal support assignment as a reduced S = 3/2 state, and reaction modeling was used to define it as a two-electron reduced “E 2 ” intermediate. Use of a MoFe protein variant, ß-188 Cys , which poises the P cluster in the oxidized P + state, demonstrated the P cluster can function as a site of photoexcited electron delivery from CdS to MoFe protein. Overall, the results establish the initial steps for how photoexcited CdS delivers electrons into MoFe protein during reduction of N 2 to ammonia, and the role of electron flux in the photochemical reaction cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Elucidating the mechanism of photochemical CO 2 reduction to CO using a cyanide-bridged di-manganese complex

The complex, [{[Mn(bpy)(CO) 3 ] 2 }(μ-CN)] + (Mn 2 CN + ), has previously been shown to photochemically reduce CO 2 to CO. The detailed mechanism behind its reactivity was not elucidated. In this work, the photoevolution of this reaction is studied in acetonitrile (MeCN) using IR and UV-vis spectroscopy. Samples were excited into the Mn I → π* bpy metal-to-ligand charge transfer (MLCT) absorption band triggering CO loss, and rapid MeCN solvent ligation at the open coordination site. It is concluded that this process occurs selectively at the Mn axial ligation site that is trans to the C-end of the bridging cyanide. Upon further photolysis, the metal–metal bonded dimeric species, [(CO) 3 (bpy)Mn–Mn(bpy)(CO) 3 ] (Mn–Mn) is observed to form under anaerobic conditions. The presence of this dimeric species coincides with the observation of CO production. When oxygen is present, CO 2 photoreduction does not occur, which is attributed to the inability of Mn 2 CN + to convert to the metal–metal bonded dimer. Photolysis experiments, where the Mn–Mn dimer is formed photochemically under argon first and then exposed to CO 2 , reveal that it is the radical species, [Mn(bpy)(CO) 3 ˙] (Mn˙), that interacts with the CO 2 . Since the presence of Mn–Mn and light is required for CO production, [Mn(bpy)(CO) 3 ˙] is proposed to be a photochemical reagent for the transformation of CO 2 to CO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Chlorophyll fluorescence imaging captures photochemical efficiency of grain sorghum (Sorghum bicolor) in a field setting

Abstract Background Photosynthesis is one of the most important biological reactions and forms the basis of crop productivity and yield on which a growing global population relies. However, to develop improved plant cultivars that are capable of increased productivity, methods that can accurately and quickly quantify photosynthetic efficiency in large numbers of genotypes under field conditions are needed. Chlorophyll fluorescence imaging is a rapid, non-destructive measurement that can provide insight into the efficiency of the light-dependent reactions of photosynthesis. Results To test and validate a field-deployed fluorescence imaging system on the TERRA-REF field scanalyzer, leaves of potted sorghum plants were treated with a photosystem II inhibitor, DCMU, to reduce photochemical efficiency (F V /F M ). The ability of the fluorescence imaging system to detect changes in fluorescence was determined by comparing the image-derived values with a handheld fluorometer. This study demonstrated that the imaging system was able to accurately measure photochemical efficiency (F V /F M ) and was highly correlated ( r = 0.92) with the handheld fluorometer values. Additionally, the fluorescence imaging system was able to track the decrease in photochemical efficiency due to treatment of DCMU over a 7 day period. Conclusions The system’s ability to capture the temporal dynamics of the plants’ response to this induced stress, which has comparable dynamics to abiotic and biotic stressors found in field environments, indicates the system is operating correctly. With the validation of the fluorescence imaging system, physiological and genetic studies can be undertaken that leverage the fluorescence imaging capabilities and throughput of the field scanalyzer.

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

Determinants of photochemical characteristics of the photosynthetic electron transport chain of maize

The photosynthetic electron transport chain (ETC) is the bridge that links energy harvesting during the photophysical reactions at one end and energy consumption during the biochemical reactions at the other. Its functioning is thus fundamental for the proper balance between energy supply and demand in photosynthesis. Currently, there is a lack of understanding regarding how the structural properties of the ETC are affected by nutrient availability and plant developmental stages, which is a major roadblock to comprehensive modeling of photosynthesis. Redox parameters reflect the structural controls of ETC on the photochemical reactions and electron transport. We conducted joint measurements of chlorophyll fluorescence (ChlF) and gas exchange under systematically varying environmental conditions and growth stages of maize and sampled foliar nutrient contents. We utilized the recently developed steady-state photochemical model to infer redox parameters of electron transport from these measurements. We found that the inferred values of these photochemical redox parameters varied with leaf macronutrient content. These variations may be caused either directly by these nutrients being components of protein complexes on the ETC or indirectly by their impacts on the structural integrity of the thylakoid and feedback from the biochemical reactions. Also, the redox parameters varied with plant morphology and developmental stage, reflecting seasonal changes in the structural properties of the ETC. Our findings will facilitate the parameterization and simulation of complete models of photosynthesis.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1973

A photochemical theory of tropospheric ozone

We present a photochemical theory for tropospheric ozone in which the methane oxidation chain constitutes a large local source. This source produces about one trillion odd oxygen molecules per square centimeter per second and implies a photochemical lifetime for ozone of about 1 day, much shorter than characteristic mixing times. The photochemical model reproduces the altitude and seasonal dependence of ozone at 30 deg N. It also gives qualitative agreement with observed day-to-day variations of the ozone density.

Chameides, W.↗
NASA NTRS1978

Photochemical-radiative damping and instability in the stratosphere. II Numerical results

In a paper by Strobel (1977), opacity effects on the joint photochemical-radiative relaxation in the stratosphere were evaluated by a linear perturbation analysis. Significant reductions in the photochemical acceleration of the thermal relaxation rate and the ozone photochemical relaxation rate were obtained in the upper stratosphere as a result of opacity changes. For very large vertical scale height ozone density perturbations, amplifying solutions were generated by large opacity changes in the O3 dissociation and heating rates. Such solutions could indicate that the stratosphere does not possess an equilibrium ozone concentration. In the present paper, some illustrative numerical calculations are presented to demonstrate the properties of the amplifying solutions. The results indicate that ungeophysically large disturbances are required and that they cease growth before attainment of geophysically interesting amplitudes, and decay to the unperturbed state.

Strobel, D. F.↗
NASA NTRS1979

Computer predictions of photochemical oxidant levels for initial precursor concentrations characteristic of southeastern Virginia

A computer study was performed with a photochemical box model, using a contemporary chemical mechanism and procedure, and a range of initial input pollutant concentrations thought to encompass those characteristic of the Southeastern Virginia region before a photochemical oxidant episode. The model predictions are consistent with the expectation of high summer afternoon ozone levels when initial nonmethane hydrocarbon (NMHC) levels are in the range 0.30-0.40 ppmC and NOx levels are in the range 0.02-0.05 ppm. Calculations made with a Lagrangian model, for one of the previously calculated cases, which had produced intermediate afternoon ozone levels, suggest that urban source additions of NMHC and NOx exacerbate the photochemical oxidant condition.

Wakelyn, N. T.↗
NASA NTRS1979

Relaxation to photochemical equilibrium of charged species within displaced air parcels in the D-region

The effects of the relaxation to photochemical equilibrium are investigated for the electrons and NO(+) ions in the upper D-region and for the electrons and several species of positive and negative ions present in the lower D-region. In the upper D-region the photochemical model includes electrons, nitric oxide, and NO(+). A self-consisting model of the equilibrium concentrations is developed for the lower D-region, which includes electrons, nitric oxide, O2(-), heavy negative and positive ions, and the oxygen species O, O3, and O2(1 delta g). At altitudes of 75 and 80 km the time dependence of the oxygen species has a significant effect on the equilibration of the electron and O2(-) concentrations. The relaxation to photochemical equilibrium proceeds by five e-folding time scales in the lower D-region, where the time required for final equilibration due to recombination is very long.

Hill, R. J.↗
NASA NTRS1981

Ozone variations and radiative-photochemical damping during a stratospheric warming

Ozone variations expected in the uppermost stratosphere and mesosphere during a warming are estimated by a photochemical calculation based on temperatures measured at 40-80 km during the February 1966 warming at Fort Churchill, Canada. A simple linearized model of radiative-photochemical relaxation is then used to describe the coupled response of ozone and temperature to a specified heating due to dynamical forcing. By comparing the joint radiative-photochemical relaxation time with that for infrared emission alone shows that the ozone perturbation induced by the warming reduces the recovery time to approximately 65% of the pure radiative value near 70 km and to 90% near 50 km. Thus, the ozone changes induced by the dynamically forced temperature increases have a significant impact on the evolution of the warming.

Frederick, J. E.↗
NASA NTRS1983

On photochemical heating of cometary comae - The cases of H2O and CO-rich comets

It is found that the effect of energy addition due to photochemical processes in the cometary coma on the heating and accelerating of the expanding neutral gas is limited by the kinematic property of the energy transfer from the energetic fragments to the bulk flow. The effective scale length of the photochemical zone for an H2O comet is estimated to be only 10% of the dimension of the collision region due to the large mass ratio of H atom and H2O molecule. When this physical property is taken into consideration, the H2O gas is found to be expanding at a highly supersonic speed. In addition, it is shown that the addition of a mixture of CO and/or CO2 molecules in a medium-bright comet with total production rate of 10 to the 29th molecules/s would not change this conclusion since the photodissiation length scales of these molecules are a factor of 10-30 larger than that of the H2O molecules. Thus, most of the CO and CO2 molecules will be dissociated outside of the collision zone without depositing the excess kinetic energy to the neutral atmosphere. However, if the gas production rate is controlled by CO or CO2, the dimension of the collision zone of a CO comet at 1 AU will be increased by a factor of seven. The photochemical heating due to CO dissociation would thus be more effective, causing the atmospheric flow to be weakly supersonic. It is concluded that the neutral gas outflows from H2O comets and CO comets could be substantially different.

Ip, W.-H.↗
NASA NTRS1987

Net ozone photochemical production over the eastern and central North Pacific as inferred from GTE/CITE 1 observations during fall 1983

The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.

Chameides, W. L.↗
NASA NTRS1988

Stratospheric responses to solar ultraviolet variations - Comparisons with photochemical models

At latitudes and altitudes where transport effects on ozone mixing ratio can be neglected, ozone and temperature responses to short-term changes in solar ultraviolet flux can be used to calculate implied bounds on two basic photochemical parameters: the odd oxygen photochemical relaxation time and the chemical sensitivity of odd oxygen to local temperature changes. Seasonally averaged values of these parameters are derived from response measurements and are compared with model calculations between 0.7 and 4 mbar at tropical latitudes. Results are in agreement within measurement and model uncertainties at all pressure levels. Model values of mean ozone and of the response of ozone to perturbations are functions of the same photochemical data. Therefore this agreement provides a constraint which should be considered when changes are proposed in model input data for the purpose of improving agreement between measured and calculated high-altitude ozone.

Hood, L. L.↗
NASA NTRS1987

Photochemical weathering and contemporary volatile loss on Mars

In an earlier series of papers by the author it was proposed that photochemical weathering of Fe(2+) in magnetite and in mafic silicates may be occurring in the contemporary surface environment with a resultant loss of O2 from the atmosphere. Morris and Lauer challenged the photochemical weathering model, proposing that oxidation by radiant heating rather than UV photoelectron emission induced oxidation may have dominated in the authors experiments. Subsequent laboratory studies of photochemical weathering of magnetite described here support the authors original proposal that UV illunimation can indeed drive the oxidation of magnetite under contemporary Martian surface conditions. The negative results of the Morris and Lauer study can now be explained.

Huguenin, R. L.↗
NASA NTRS1989

Model estimates of enhanced photochemical production of ozone resulting from convective transport of precursors

Vertical profiles of net photochemical ozone production rates and total tropospheric column production rates were estimated using two models, a simple photochemical box model and a time-dependent one-dimensional transport/kinetics model. Photochemical production of ozone is found to dominate over destruction throughout the vertical extent of the troposphere over the central United States during typical summertime convective conditions. The column net production can be enhanced by the transport of the ozone precursors NO and NMHC from the boundary layer to the free troposphere by convective activity.

Pickering, Kenneth E.↗