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High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri

Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

Non-NASA Center

3D Photocatalytic Air Processor for Dramatic Reduction of Life Support Mass and Complexity

To dramatically reduce the cost and risk of CO2 management systems in future extended missions, we have conducted preliminary studies on the materials and device development for advanced "artificial photosynthesis" reaction systems termed the High Tortuosity PhotoElectroChemical (HTPEC) system. Our Phase I studies have demonstrated that HTPEC operates in much the same way a tree would function, namely directly contacting the cabin air with a photocatalyst in the presence of light and water (as humidity) to immediately conduct the process of CO2 reduction to O2 and useful, "tunable" carbon products. This eliminates many of the inefficiencies associated with current ISS CO2 management systems. We have laid the solid foundation for Phase II work to employ novel and efficient reactor geometries, lighting approaches, 3D manufacturing methods and in-house grown novel catalytic materials.The primary objective of the proposed work is to demonstrate the scientific and engineering foundation for light-activated, compact devices capable of converting CO2 to O2 and mission-relevant carbon compounds. The proposed HTPEC CO2 management system will demonstrate a novel pathway with high efficiency and reliability in a compact, lightweight reactor architecture. The proposed HTPEC air processing concept can be developed in multiple architectures, such as centralized processing as well as "artificial leaves" distributed throughout the cabin that utilize pre-existing cabin ventilation (wind). Additionally, HTPEC can be deployed with spectrally tunable collection channels for selectable product generation. HTPEC employs light as its only energy source to remove and convert waste CO2 using a non-toxic composite catalyst.We have demonstrated in the Phase I studies the production, tunability and robustness of the novel composite catalysts following the preliminary work in the Chen laboratory. Additionally, we have designed, fabricated and tested all components of HTPEC device with active materials, including flow modeling to optimize flow mixing and pressure drop as well as the production of ethylene and other larger hydrocarbons. To best determine how this technology could be implemented, we also performed system integration optimization and trade studies. This includes parameters such as mass, volume, power in relation to selected mission configurations, CO2 delivery methods and light source/delivery approaches.

Artificial Photosynthesis

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

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

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

Diffuse-Illumination Systems for Growing Plants

Agriculture in both terrestrial and space-controlled environments relies heavily on artificial illumination for efficient photosynthesis. Plant-growth illumination systems require high photon flux in the spectral range corresponding with plant photosynthetic active radiation (PAR) (400 700 nm), high spatial uniformity to promote uniform growth, and high energy efficiency to minimize electricity usage. The proposed plant-growth system takes advantage of the highly diffuse reflective surfaces on the interior of a sphere, hemisphere, or other nearly enclosed structure that is coated with highly reflective materials. This type of surface and structure uniformly mixes discrete light sources to produce highly uniform illumination. Multiple reflections from within the domelike structures are exploited to obtain diffuse illumination, which promotes the efficient reuse of photons that have not yet been absorbed by plants. The highly reflective surfaces encourage only the plant tissue (placed inside the sphere or enclosure) to absorb the light. Discrete light sources, such as light emitting diodes (LEDs), are typically used because of their high efficiency, wavelength selection, and electronically dimmable properties. The light sources are arranged to minimize shadowing and to improve uniformity. Different wavelengths of LEDs (typically blue, green, and red) are used for photosynthesis. Wavelengths outside the PAR range can be added for plant diagnostics or for growth regulation

May, George

Predicting lettuce canopy photosynthesis with statistical and neural network models

An artificial neural network (NN) and a statistical regression model were developed to predict canopy photosynthetic rates (Pn) for 'Waldman's Green' leaf lettuce (Latuca sativa L.). All data used to develop and test the models were collected for crop stands grown hydroponically and under controlled-environment conditions. In the NN and regression models, canopy Pn was predicted as a function of three independent variables: shootzone CO2 concentration (600 to 1500 micromoles mol-1), photosynthetic photon flux (PPF) (600 to 1100 micromoles m-2 s-1), and canopy age (10 to 20 days after planting). The models were used to determine the combinations of CO2 and PPF setpoints required each day to maintain maximum canopy Pn. The statistical model (a third-order polynomial) predicted Pn more accurately than the simple NN (a three-layer, fully connected net). Over an 11-day validation period, average percent difference between predicted and actual Pn was 12.3% and 24.6% for the statistical and NN models, respectively. Both models lost considerable accuracy when used to determine relatively long-range Pn predictions (> or = 6 days into the future).

Non-NASA Center

Search for and investigation of extraterrestrial forms of life

Correct combinations of remote, analytic, and functional methods and measuring devices for detecting extraterrestrial life are elaborated. Considered are techniques and instruments available both on earth and aboard spacecraft and artificial planetary satellites. Emphasis is placed on the abiogenetic synthesis of organic compounds formed in photosynthesis on Mars.

Rubin, A. B.

Enhancement of efficiency in the use of light for cultivation of plants in controlled ecological systems

The problems of plant cultivation with the use of artificial lighting are related to energetics and, initially, to the lack of effective sources for photosynthesis, secondly to the necessity to supply a system with a considerable power in the form of light energy and to remove transformed thermal energy, and finally to economic considerations. These problems are solved by three ways: by the choice of effective radiation sources, design approaches, and technological methods of cultivation. Here we shall consider the first two ways.

Mashinsky, A. L.

Anaerobic Expression and Purification of Holo-CCIS, an Artificial Iron-sulfur Protein

Iron-sulfur proteins are ubiquitous among all living organisms and are indispensable for almost all metabolic pathways ranging from photosynthesis, respiration, nitrogen, and carbon dioxide cycles. The iron-sulfur clusters primarily serve as electron acceptors and donors and transfer electrons to active sites of various enzymes, thus driving the energy metabolism. Prokaryotes like E. coli have ISC and SUF pathways that help in the assembly and maturation of iron-sulfur proteins. These ironsulfur proteins, especially with [4Fe-4S] clusters, are highly sensitive to molecular oxygen, and it would be advantageous if the de novo proteins and native proteins having iron-sulfur binding sites are expressed and isolated under anaerobic conditions. Bacterially assembled iron-sulfur proteins, when isolated and purified anaerobically, exhibit improved biochemical and biophysical stabilities in comparison to the counterparts expressed and purified aerobically and reconstituted under anaerobic conditions. This protocol outlines the expression and purification of the artificial protein, Coiled-Coil IronSulfur (CCIS). It may be deployed to both natural and artificial [4Fe-4S] proteins when heterologously expressed in E. coli.

Bhanu P. Jagilinki

Electrochemical Recycling of CO2

Carbon dioxide (CO2) is a molecule that plays multiple roles in our universe. Currently, its impact on global warming has rightfully given CO2 a label as a harmful waste product that must be amply handled. Nonetheless, under other circumstances, and from other perspectives, CO2 could be regarded as a valuable resource. As example, in nature CO2 is an essential building block in photosynthesis ultimately yielding molecules and materials that we harvest for numerous applications ranging from energy storage and construction to medicines and food. In a similar manner, there is a growing interest to utilize atmospheric CO2 to generate renewable fuels and platform chemicals through artificial processes. These processes can replace fossil based industrial processes on earth alleviating climate impact, but they can also find uses far away from our planet. In space, CO2 is an important source of precious oxygen, however, it can also serve as feedstock for carbon-based molecules and materials that are needed to sustain societies at distant planets such as Mars. In this presentation, I will discuss the contemporary understanding of electrochemical reduction of CO2 for selective production of desired molecules. We will zoom in to the very atomic scale to gain mechanistic understanding of how the structure and composition of the cathode electrode affects product distributions. This information is used as guide in the design of new materials that convert CO2 more efficiently and more selectively. On this basis, opportunities for recycling CO2 under different conditions will be discussed, as will remaining challenges for the ultimate application towards the sustainable human living on earth and in space.

electrochemistry

Photosynthesis-dependent Isoprene Emission from Leaf to Planet in a Global Carbon-chemistry-climate Model

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the FarquharBallBerry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50 of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 6496) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr1 that increases by 30 in the artificial absence of plant water stress and by 55 for potential natural vegetation.

photosynthesis

The Effects of Low Sulfate Concentrations on Modern Microbial Mat Communities: A Long Term Manipulation

Microbial mats were widespread during the first ca. 2 Ga. of our biosphere's history. To better understand microbial ecosystems and their biomarkers under the low sulfate levels present in early oceans, we attempted a long-term (ca. 1 year) manipulation of sulfate in modem mats. Mats collected from salt ponds at Guerrero Negro, Baja Calif. Sur were incubated in a Greenhouse "Collaboratory" at Ames. Mats were maintained in artificial seawater brine containing either: 1) sulfate levels normal for these mats (70 mM), or 2) brine in which sulfate was replaced by chloride. Sulfate concentrations in the "low sulfate" brine gradually approached their lowest (to date) value of 0. 1 mM as sulfate was consumed and/or diffused out of the mat over a period of ca. 4 months. During that period of time, a number of differences between the treatments emerged. Relative to the "low sulfate" mats, "normal sulfate" mats had: 1) lower consumption of oxygen in the lower levels of the mat, 2) higher efficiencies of oxygenic photosynthesis, and 3) higher rates of nitrogen fixation. Rates of methane production by the mats increased greatly as sulfate concentrations fell below ca. 0.2 mM. In contrast, "low" and "normal" sulfate mats had similar net rates of exchange of O2 and dissolved inorganic C between the mats and overlying water. Reduced sulfate levels have diverse impacts upon these ecosystems.

Bebout, Brad

Development of a Photosynthesis Measurement Chamber under Different Airspeeds for Applications in Future Space Crop-Production Facilities

Space crop production systems are being developed to grow fresh produce in-situ to supplement the astronauts’ diet, but the required ventilation rates for crops in different gravity environments remains poorly understood. The reduction or lack of buoyancy-driven convection in reduced gravity environments leads to impaired gas exchange (CO2 absorption, water transpiration and O2 release) at the leaf surface if no extra ventilation is provided, and this could lead to a reduction in biomass production in the long run. To better characterize the influence of different airspeeds on photosynthesis and be able to model this in low gravity, a chamber was designed to interface with a LI-6800 portable photosynthesis system. This paper details the design of this chamber, specifically made to measure whole-plant and small canopy gas exchange at different airspeeds. The fans provide turbulent mixing in the chamber to ensure that it behaves like a continuous stirred tank reactor (CSTR)and that the residence time distribution (RTD) is the same for any fan speed; the computational fluid dynamic (CFD) model of the gas domain (the air in the chamber) hence uses a k-omega turbulence model. An airflow map of the chamber was created using anemometer measurements for the different airspeeds tested, and this was used together with the CFD simulation results to relate the experimentally measured fan outputs to actual airspeeds on top of an artificial plant. Environmental parameters (air temperature, relative humidity, CO2level) are controlled by the LI-6800. This work was funded by NASA Space Biology through the NASA postdoctoral program / USRA.

Lucie Poulet

A new relative referencing method for crop monitoring using chlorophyll fluorescence

The measurement of plant chlorophyll fluorescence has been used for many years as a method to monitor a plant's health status. These types of methods have been mostly relegated to the laboratory. The newly developed Relative Referencing Method allows for the measurement of chlorophyll fluorescence under artificial lighting conditions. The fluorescence signal can be determined by first taking a reference signal measurement, then a second measurement with an additional fluorescence excitation source. The first signal can then be subtracted from the second and the plant's chlorophyll fluorescence due to the second lighting source can be determined. With this simple approach, a photosynthesizing plant can be monitored to detect signs of water stress. Using this approach experiments on tomato plants have shown that it was possible to detect water stress, while the plants were continuously illuminated by fluorescent lamps. This method is a promising tool for the remote monitoring of crops grown in a CELSS-type application. Published by Elsevier Science Ltd on behalf of COSPAR.

Plant Physiology