Search NASA⌕ Search

SEARCH · Search NASA

Results for “artificial photosynthesis”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Evolution from Tunneling to Hopping Mediated Triplet Energy Transfer from Quantum Dots to Molecules

Efficient energy transfer is particularly important for multiexcitonic processes like singlet fission and photon upconversion. Observation of the transition from short-range tunneling to long-range hopping during triplet exciton transfer from CdSe nanocrystals to anthracene is reported here. This is firmly supported by steady- state photon upconversion measurements, a direct proxy for the efficiency of triplet energy transfer (TET), as well as transient absorption measurements. When phenylene bridges are initially inserted between a CdSe nanocrystal donor and anthracene acceptor, the rate of TET decreases exponentially, commensurate with a decrease in the photon upconversion quantum efficiency from 11.6% to 4.51% to 0.284%, as expected from a tunneling mechanism. However, as the rigid bridge is increased in length to 4 and 5 phenylene units, photon upconversion quantum efficiencies increase again to 0.468% and 0.413%, 1.5–1.6 fold higher than that with 3 phenylene units (using the convention where the maximum upconversion quantum efficiency is 100%). This suggests a transition from exciton tunneling to hopping, resulting in relatively efficient and distance-independent TET beyond the traditional 1 nm Dexter distance. Transient absorption spectroscopy is used to confirm triplet energy transfer from CdSe to transmitter, and the formation of a bridge triplet state as an intermediate for the hopping mechanism. Lastly, this first observation of the tunneling-to-hopping transition for long-range triplet energy transfer between nanocrystal light absorbers and molecular acceptors suggests that these hybrid materials should further be explored in the context of artificial photosynthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

High-Energy Hybridized States Enable Long-Lived Hot Electrons in Cobaloxime-Silicon Nanocrystal System

Strong electronic coupling is achieved between the molecular catalyst cobaloxime ([Co]) and silicon nanocrystals (Si NCs) bridged by an ethylenepyridine group derived from vinylpyridine (vpy) covalently bound to the Si NC surface (Si-vpy-[Co]). The ethylenepyridine tether in Si-vpy-[Co] is key to dramatic changes to the system’s physical properties which are not observed in the corresponding formylpyridine (fpy) system (Si-fpy-[Co]) consistent with strong electronic coupling previously observed only in dark electrochemical systems. UV−vis absorption spectroscopy reveals new [Co]-centered electronic states in Si-vpy-[Co], and transient absorption spectroscopy finds a strong absorption feature appearing within 250 fs and persisting for at least 5 ns. Astoundingly, spectroelectrochemical measurements reveal that this absorption feature is consistent with both the singly reduced [Co] − and doubly reduced [Co] 2− complexes, leading to the conclusion that these long-lived charges are derived from high-energy “hot” electrons residing in [Co]-centered states. Detailed analysis using cyclic voltammetry, spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and density functional theory (DFT) calculations provides insight into the unique electronic structure created in Si-vpy-[Co]. DFT reveals that the new electronic states arise from hybridization between deep Si NC band states and high-energy molecular orbitals of the ethylenepyridine tether and the [Co] catalyst and are facilitated by σ-bonding character at the ethylenepyridine linkage. This study demonstrates that strong electronic coupling achieved through precise molecular chemistry can change the paradigm of otherwise fixed energy levels in hybrid photoelectrochemical systems for artificial photosynthesis and related applications.

14 SOLAR ENERGY↗
DOE OSTI2020

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

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

Photocatalytic water splitting

With the goal of achieving large-scale H 2 production from renewable resources, water splitting into H 2 and O 2 using semiconductor photocatalysts (sometimes called artificial photosynthesis) has been studied for five decades. Unfortunately, the lack of rigour and reproducibility in the data collection and analysis of experimental results has hindered progress in the field. This Primer provides a comprehensive overview of proper characterization and evaluation of photocatalysts for overall water splitting. In particular, the Primer covers various pitfalls in photocatalysis research, best practices for reproducibility and reliable methods for conducting rigorous experiments. As a result, the recommendations are intended to reduce false positives in the literature and to promote progress towards a practical technology for producing H 2 from water by using sunlight.

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

Energetics of CO 2 and H 2 O adsorption on alkaline earth metal doped TiO 2

The process of CO 2 and H 2 O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO 2 and H 2 O adsorption on TiO 2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO 2 surface affinity to CO 2 and H 2 O, TiO 2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO 2 nanoparticles, both CO 2 and subsequent H2O adsorption amounts could be increased. CO 2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

On the design and performance of InGaN/Si double-junction photocathodes

Via a combined theoretical and experimental study, we have investigated the synthesis and performance characteristics of InGaN/Si double-junction photoelectrochemical (PEC) water splitting devices, which promise a theoretical solar-to-hydrogen conversion efficiency ~30% under AM 1.5G one-sun illumination. The double-junction photocathodes consist of a p + -InGaN top light absorber and a Si bottom p-n junction, which are connected through a nanowire tunnel junction. The effect of indium composition of the top light absorber as well as the impact of p-type Mg dopant incorporation on the PEC performance was studied. Experimentally, the sample with 32% indium composition showed a maximum photocurrent density of ~9 mA/cm 2 at 0.4 mV vs reverse hydrogen electrode (RHE) with applied bias photon-to-current efficiency (ABPE) of ~9.5%. An optimum p-type doping level ~1 × 10 17 cm -3 was also identified, which results in the best device performance as a result of optimum surface band bending as well as vertical charge carrier (hole) transport. These results also show a good agreement with our theoretical analysis. This work provides significant insights in advancing the design and development of high efficiency PEC devices for artificial photosynthesis using industry ready materials, e.g., Si and GaN, to achieve large-scale, low-cost onsite hydrogen fuel production.

42 ENGINEERING↗
DOE OSTI2022

Design and characterization of surface molecular assemblies for the preparation of solar fuels

A key issue in solar energy conversion is the utilization of solar energy for the preparation of solar fuels. In this area, artificial photosynthesis offers promising approaches for the conversion of H 2 O and CO 2 into usable solar fuels. This review highlights both the design and characterization of surface molecular assemblies for the preparation of solar fuels. It includes mechanistic summaries of the details of the underlying surface chemical reactions including water oxidation and proton/water reduction. The surface mechanisms are shown to integrate molecular reactivity with surface electron transfer in integrated assemblies that lead to impressive efficiencies for water oxidation and proton or CO 2 reduction.

catalysts and catalysis↗
DOE OSTI2024

Structural and optical characterization of dilute Bi-doped GaN nanostructures grown by molecular beam epitaxy

We have carried out detailed studies on the epitaxy and characterization of dilute Bi-doped GaN nanostructures. A comprehensive investigation of Bi-doped GaN nanowires and quasi-film epitaxial growth conditions has been performed. Scanning electron microscopy studies show that lowering the GaBiN growth temperature causes gradual changes in top c-plane nanowire morphology due to the incremental incorporation of foreign Bi atoms. This trend is further substantiated by the secondary ion mass spectroscopy analysis of a multi-layer Bi-doped GaN quasi-film. However, it is also found that the amount of Bi incorporation into the GaN lattice is relatively independent of the N2 flow rate variation under the growth conditions investigated. Furthermore, room-temperature micro-Raman spectra show that there are additional peaks near 530, 650, and 729 cm−1 wave numbers in the Bi-doped GaN samples, which can primarily be attributed to Bi local vibrational modes, indicative of a small amount of Bi incorporation in the GaN lattice. Moreover, phonon calculations with density functional theory indicate that Bi replacing the N sites is the likely origin of the experimentally measured Raman modes. X-ray photoelectron spectroscopy measurements have also been obtained to deduce the electronic interaction between the Bi dopant atom and the GaN nanostructure. Such one-dimensional nanowires permit the synthesis of dislocation-free highly mismatched alloys due to strain relaxation, allowing efficient light absorption and charge carrier extraction that is relevant for solar energy harvesting and artificial photosynthesis.

Materials Science↗
DOE OSTI2020

Addressing the challenge of carbon-free energy

This century will witness a major transformation in how energy is acquired, stored, and utilized globally. The impetus for this change comes from the deep impacts that both developed and developing societies have had on our planet's environment during the past century, and the projections going forward of what will happen if we do not act transformativelywithin the next 2 decades. This paper describes the basis for a meeting held in October 2018 on the need for decarbonization in our energy landscape, and specifically the status and challenges of the science that provides the foundation for such technology. Within the realm of decarbonization in energy generation lies the science of solar energy conversion using new or improved photovoltaic materials and artificial photosynthesis for water splitting and other energy-storing reactions. The intimately related issue of renewable energy storage is being addressed with new strategies, materials, and approaches under current investigation and development. The need to improve the interactions between scientists working on these connected but separately considered challenges and on the transition of scientific achievement to practical application was also addressed, with specific efforts enumerated.

climate change↗
DOE OSTI2023

Shewanella oneidensis MR-1 respires CdSe quantum dots for photocatalytic hydrogen evolution

Living bio-nano systems for artificial photosynthesis are of growing interest. Typically, these systems use photoinduced charge transfer to provide electrons for microbial metabolic processes, yielding a biosynthetic solar fuel. Here, we demonstrate an entirely different approach to constructing a living bio-nano system, in which electrogenic bacteria respire semiconductor nanoparticles to support nanoparticle photocatalysis. Semiconductor nanocrystals are highly active and robust photocatalysts for hydrogen (H 2 ) evolution, but their use is hindered by the oxidative side of the reaction. In this system, Shewanella oneidensis MR-1 provides electrons to a CdSe nanocrystalline photocatalyst, enabling visible light-driven H 2 production. Unlike microbial electrolysis cells, this system requires no external potential. Illuminating this system at 530 nm yields continuous H 2 generation for 168 h, which can be lengthened further by replenishing bacterial nutrients.

Science & Technology - Other Topics↗
DOE OSTI2020

Science Opportunities and Capabilities Enabled by LCLS-II and LCLS-II HE

X-Ray Science with LCLS-II and LCLS-II HE: Chemical dynamics: Reaction dynamics, charge transfer, molecular photocatalysts, natural & artificial photosynthesis; Catalysis: Homogeneous and heterogeneous catalysis, interfacial & geo/environmental chemistry; Materials Physics: Heterogeneity, spontaneous fluctuations, nonequilibrium dynamics, extreme environments; Quantum Materials: Emergent phenomena & collective excitations; Biological Function & Structural Dynamics: Dynamics in physiological environments.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Design, Synthesis, and Utility of Defined Molecular Scaffolds

A growing theme in chemistry is the joining of multiple organic molecular building blocks to create functional molecules. Diverse derivatizable structures—here termed “scaffolds” comprised of “hubs”—provide the foundation for systematic covalent organization of a rich variety of building blocks. This review encompasses 30 tri- or tetra-armed molecular hubs (e.g., triazine, lysine, arenes, dyes) that are used directly or in combination to give linear, cyclic, or branched scaffolds. Each scaffold is categorized by graph theory into one of 31 trees to express the molecular connectivity and overall architecture. Rational chemistry with exacting numbers of derivatizable sites is emphasized. The incorporation of water-solubilization motifs, robust or self-immolative linkers, enzymatically cleavable groups and functional appendages affords immense (and often late-stage) diversification of the scaffolds. Altogether, 107 target molecules are reviewed along with 19 syntheses to illustrate the distinctive chemistries for creating and derivatizing scaffolds. The review covers the history of the field up through 2020, briefly touching on statistically derivatized carriers employed in immunology as counterpoints to the rationally assembled and derivatized scaffolds here, although most citations are from the past two decades. The scaffolds are used widely in fields ranging from pure chemistry to artificial photosynthesis and biomedical sciences.

Sato, Daisuke (ORCID:0000000305472659)↗
NASA NTRS2009

NASA Tech Briefs, September 2009

opics covered include: Filtering Water by Use of Ultrasonically Vibrated Nanotubes; Computer Code for Nanostructure Simulation; Functionalizing CNTs for Making Epoxy/CNT Composites; Improvements in Production of Single-Walled Carbon Nanotubes; Progress Toward Sequestering Carbon Nanotubes in PmPV; Two-Stage Variable Sample-Rate Conversion System; Estimating Transmitted-Signal Phase Variations for Uplink Array Antennas; Board Saver for Use with Developmental FPGAs; Circuit for Driving Piezoelectric Transducers; Digital Synchronizer without Metastability; Compact, Low-Overhead, MIL-STD-1553B Controller; Parallel-Processing CMOS Circuitry for M-QAM and 8PSK TCM; Differential InP HEMT MMIC Amplifiers Embedded in Waveguides; Improved Aerogel Vacuum Thermal Insulation; Fluoroester Co-Solvents for Low-Temperature Li+ Cells; Using Volcanic Ash to Remove Dissolved Uranium and Lead; High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell; Silicon Wafer-Scale Substrate for Microshutters and Detector Arrays; Micro-Horn Arrays for Ultrasonic Impedance Matching; Improved Controller for a Three-Axis Piezoelectric Stage; Nano-Pervaporation Membrane with Heat Exchanger Generates Medical-Grade Water; Micro-Organ Devices; Nonlinear Thermal Compensators for WGM Resonators; Dynamic Self-Locking of an OEO Containing a VCSEL; Internal Water Vapor Photoacoustic Calibration; Mid-Infrared Reflectance Imaging of Thermal-Barrier Coatings; Improving the Visible and Infrared Contrast Ratio of Microshutter Arrays; Improved Scanners for Microscopic Hyperspectral Imaging; Rate-Compatible LDPC Codes with Linear Minimum Distance; PrimeSupplier Cross-Program Impact Analysis and Supplier Stability Indicator Simulation Model; Integrated Planning for Telepresence With Time Delays; Minimizing Input-to-Output Latency in Virtual Environment; Battery Cell Voltage Sensing and Balancing Using Addressable Transformers; Gaussian and Lognormal Models of Hurricane Gust Factors; Simulation of Attitude and Trajectory Dynamics and Control of Multiple Spacecraft; Integrated Modeling of Spacecraft Touch-and-Go Sampling; Spacecraft Station-Keeping Trajectory and Mission Design Tools; Efficient Model-Based Diagnosis Engine; and DSN Simulator.

Source record↗
NASA NTRSDate not supplied

A New Vision and A More Rational Process Will Advance Space Life Support Through Better Projects

Many space life support assumptions are obviously mistaken but they are generally accepted because they mutually support each other and because they advance a mistaken futuristic vision of closed human ecosystems in space. Many projects have been mistakenly selected to increase life support system closure or reduce launch mass in order to implement this impractical vision. Project members rarely challenge their project’s assumptions and guiding vision. Systems engineering including cost, reliability, risk, and system trade-offs has been very strongly discouraged to prevent rational criticism of these dubious assumptions, the projects, and the ecosystem vision. A more realistic vision can define better near term life support goals and future aspirations that will improve mission support and increase public interest. Given more realistic goals, it will be possible to develop effective technical alternatives, use open rational project selection methods, conduct professional project management, and make swifter progress in the inevitable human advance into space. The current unworkable human space settlement scenario involves moon visits and permanent bases, zero gravity trips to Mars, Mars visits and bases, all leading to extensive human settlements on the moon and Mars. This is unrealistic because the moon and Mars have less than Earth normal gravity and high radiation that can seriously damage human health. A better alternative would use rotating space colonies that produce Earth gravity and are radiation shielded. The attractive fantasy of reproducing terrestrial ecology in space should be replaced by the idea of building a closed system based on advancing technology such as artificial photosynthesis. Past mistaken projects include growing plants for food to replicate terrestrial food sources, recovering small amounts of water from difficult to process waste to achieve high system closure, and using newly designed, lighter, but unreliable hardware to reduce launch mass. The political process supporting the false assumptions, projects, and vision has deliberately prevented the usual systems engineering and cost-benefit analysis. We are going to do much better.

Harry W. Jones↗
NASA NTRSDate not supplied

American Society of Plant Biologists Plenary Symposium Overview Presentation

NASA’s Artemis program in collaboration with international space agencies, and various commercial partners, marks the return of humankind to the Moon. Unlike the Apollo lunar missions from fifty years ago, Artemis will set the stage for the continuous presence of humans on the Moon and pave a path for the journey to Mars and beyond. Plants will be an essential component of habitation systems that will enable humans to thrive on both the lunar and Mars surface, as well as space transit vehicles because of their nutritional and psychological benefits. Furthermore, plants will be valued in environmental control and life support systems because they generate oxygen, remove carbon dioxide, and recycle water and waste. However, an in-depth understanding of how plants and their associated microbial communities adapt to the harsh and confined environment of deep space is essential before they can be effectively used for long-duration space missions. This plenary symposium will address challenges and present potential solutions to growing plants in space. The four speakers will cover a broad range of topics, including mechanistic studies on fern resurgence after asteroid-triggered mass extinction events, artificial photosynthesis for space agriculture, and how the plant microbiome and an understanding of plant-pathogen dynamics in microgravity can guide crop production strategies in space.

Plant Space Biology↗
DOE OSTI2026

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗
DOE OSTI2020

Symmetry Effects in Photoinduced Electron Transfer in Chlorin-Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region

In donor–acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor–acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD-DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling. This surprising observation provides the first experimental evidence for theoretically predicted adiabatic suppression of PET in MIR, which unambiguously controlled solely by symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗