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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 199 records · Page 11

Optical Testing of Retroreflectors for Cryogenic Applications

A laser tracker (LT) is an important coordinate metrology tool that uses laser interferometry to determine precise distances to objects, points, or surfaces defined by an optical reference, such as a retroreflector. A retroreflector is a precision optic consisting of three orthogonal faces that returns an incident laser beam nearly exactly parallel to the incident beam. Commercial retroreflectors are designed for operation at room temperature and are specified by the divergence, or beam deviation, of the returning laser beam, usually a few arcseconds or less. When a retroreflector goes to extreme cold (.35 K), however, it could be anticipated that the precision alignment between the three faces and the surface figure of each face would be compromised, resulting in wavefront errors and beam divergence, degrading the accuracy of the LT position determination. Controlled tests must be done beforehand to determine survivability and these LT coordinate errors. Since conventional interferometer systems and laser trackers do not operate in vacuum or at cold temperatures, measurements must be done through a vacuum window, and care must be taken to ensure window-induced errors are negligible, or can be subtracted out. Retroreflector holders must be carefully designed to minimize thermally induced stresses. Changes in the path length and refractive index of the retroreflector have to be considered. Cryogenic vacuum testing was done on commercial solid glass retroreflectors for use on cryogenic metrology tasks. The capabilities to measure wavefront errors, measure beam deviations, and acquire laser tracker coordinate data were demonstrated. Measurable but relatively small increases in beam deviation were shown, and further tests are planned to make an accurate determination of coordinate errors.

Ohl, Raymond G.↗

Dynamic Boundary Microgrids Under Privatization Considerations

Microgrids have physical, electrical, and logical (data, network, and ownership) boundaries. To power unserved customer loads during an outage, microgrids can extend the traditional operational boundaries. This can become complex when considering microgrid-to-microgrid (M2M) interactions where sensitive information such as competitive microgrid operational data is not shared. This work proposes an optimization method coordinated between microgrid controllers and distribution management systems that limits data sharing. The method involves a competitive bidding strategy that maximizes unserved load coverage while minimizing resource utilization and sensitive operational data sharing among entities. The work is validated on a two-microgrid system with photovoltaic and energy storage systems and curves of load derived from real world residential buildings datasets. Results show that the proposed method, when applied for three distinct use cases of energy storage sufficiency to cover the predefined boundary and/or the expanded boundary, can successfully select and bid the available load coverage.

Starke, Michael [ORNL] (ORCID:0000000221211195)↗

Leaf-level physiological strategies related to productivity and plasticity of Populus in the Southeastern United States

Introduction: Populus and its hybrids are attractive bioenergy crops and the southeastern United States has broad ability to supply bioenergy markets with woody biomass. Breeding and hybridization have led to superior eastern cottonwood (Populus deltoides W. Bartram ex Marshall) and hybrid poplars adapted to a wide variety of site types not suited for agricultural production. In order to maximize productivity and minimize inputs, genotypes need to efficiently use available site resources and tolerate environmental stresses. In addition, we need to determine plasticity of traits and their coordination across sites to select traits that will broadly characterize genotypes. Therefore, our study objectives were to determine (1) which leaf traits were correlated with growth, (2) if traits and genotypes exhibited significant plasticity across sites, and (3) how traits were coordinated within and across sites and Populus taxa. Methods: We measured trees at two sites in northeastern Mississippi, United States: one upland and one alluvial terrace site. Genotypes included eastern cottonwoods as well as F 1 crosses of eastern cottonwood and P. maximowiczii (Henry), P. nigra (L.) and P. trichocarpa (Torr. & Gray). Results: We found that sites differed in which leaf traits were correlated with productivity; with water use efficiency specifically being positively correlated with growth at an alluvial terrace site, but negatively correlated with growth at an upland site. Tree height growth, leaf isotope composition (δ 13 C and δ 15 N), as well as leaf mass per area (LMA) exhibited the least plasticity across sites, while physiological gas exchange parameters and leaf nitrogen concentration exhibited the highest plasticity. Broadly across taxa, leaf carbon isotope ratios were correlated with intrinsic water use efficiency, and stomatal conductance was positively correlated with photosynthetic nitrogen use efficiency across sites, while leaf nitrogen isotope ratios exhibited contrasting relationships with leaf nitrogen concentration. Discussion: Overall, these results allow us to refine selections of productive genotypes based on site conditions and site-specific relationships with physiological parameters to better match Populus taxa with sites and landowner objectives.

bioenergy feedstocks↗

The whole earth telescope - A new astronomical instrument

A new multimirror ground-based telescope for time-series photometry of rapid variable stars, designed to minimize or eliminate gaps in the brightness record caused by the rotation of the earth, is described. A sequence of existing telescopes distributed in longitude, coordinated from a single control center, is used to measure designated target stars so long as they are in darkness. Data are returned by electronic mail to the control center, where they are analyzed in real time. This instrument is the first to provide data of continuity and quality that permit true high-resolution power spectroscopy of pulsating white dwarf stars.

Nather, R. E.↗

Construction of Solar-Wind-Like Magnetic Fields

Fluctuations in the solar wind fields tend to not only have velocities and magnetic fields correlated in the sense consistent with Alfven waves traveling from the Sun, but they also have the magnitude of the magnetic field remarkably constant despite their being broadband. This paper provides, for the first time, a method for constructing fields with nearly constant magnetic field, zero divergence, and with any specified power spectrum for the fluctuations of the components of the field. Every wave vector, k, is associated with two polarizations the relative phases of these can be chosen to minimize the variance of the field magnitude while retaining the\random character of the fields. The method is applied to a case with one spatial coordinate that demonstrates good agreement with observed time series and power spectra of the magnetic field in the solar wind, as well as with the distribution of the angles of rapid changes (discontinuities), thus showing a deep connection between two seemingly unrelated issues. It is suggested that using this construction will lead to more realistic simulations of solar wind turbulence and of the propagation of energetic particles.

Roberts, Dana Aaron↗

Towards the Development of a Global, Satellite-Based, Terrestrial Snow Mission Planning Tool

A global, satellite-based, terrestrial snow mission planning tool is proposed to help inform experimental mission design with relevance to snow depth and snow water equivalent (SWE). The idea leverages the capabilities of NASA's Land Information System (LIS) and the Tradespace Analysis Tool for Constellations (TAT-C) to harness the information content of Earth science mission data across a suite of hypothetical sensor designs, orbital configurations, data assimilation algorithms, and optimization and uncertainty techniques, including cost estimates and risk assessments of each hypothetical permutation. One objective of the proposed observing system simulation experiment (OSSE) is to assess the complementary or perhaps contradictory information content derived from the simultaneous collection of passive microwave (radiometer), active microwave (radar), and LIDAR observations from space-based platforms. The integrated system will enable a true end-to-end OSSE that can help quantify the value of observations based on their utility towards both scientific research and applications as well as to better guide future mission design. Science and mission planning questions addressed as part of this concept include: What observational records are needed (in space and time) to maximize terrestrial snow experimental utility? How might observations be coordinated (in space and time) to maximize this utility? What is the additional utility associated with an additional observation? How can future mission costs be minimized while ensuring Science requirements are fulfilled?

Mission Desig↗

UTM and D-NET: NASA and JAXA's Collaborative Research on Integrating Small UAS with Disaster Response Efforts

Natural disasters, such as flooding, wildfire, hurricane, tornadoes, earthquakes and tsunamis, pose challenges in preserving human life and minimizing the damages to a region. During catastrophic events, timely response of disaster relief personnel, an efficient deployment of resources in the recovery effort, and coordinated information sharing amongst different relief agencies can make a substantial difference in responding to those impacted by the disaster. Many relief activities currently utilize both ground personnel and manned airborne assets during different phases of the disaster response. Typically, multiple organizations support relief activities and this often creates logistics coordination challenges between agencies which can result in wasted time or resources. The Japan Aerospace Exploration Agency (JAXA) has been developing an "Integrated aircraft operation system for disaster relief (D-NET)", which assists collection and sharing of disaster information through the integrated operation of aircraft such as helicopters, aircraft, and satellites, for efficient and safe rescue operations by disaster relief aircraft. Due to the advancement in unmanned aircraft systems (UAS) technologies, public safety organizations have started incorporating small UAS (sUAS) as an asset in their disasters response activities. To address the airspace integration challenges of the influx of sUAS in the United States the National Aeronautics and Space Administration (NASA), under the UAS Traffic Management (UTM) project, has been engaged in research to enable large-scale commercial applications of sUAS operating in low altitude airspace. This paper presents the integration of D-NET, which incorporate sUAS in the planning, information sharing, and operation support of disasters response activities, and UTM, which provides airspace management to enable large scale high density operations. The integration of the DNET and UTM systems enables coordination, data sharing, and airspace management to improve the timeliness of the disaster response, enable relief organization to reduce cost and overhead by using UAS assets and still maintain airspace safety during the relief activities.

UTM↗

Airborne Antenna System for Minimum-Cycle-Slip GPS Reception

A system that includes a Global Positioning System (GPS) antenna and associated apparatus for keeping the antenna aimed upward has been developed for use aboard a remote-sensing-survey airplane. The purpose served by the system is to enable minimum- cycle-slip reception of GPS signals used in precise computation of the trajectory of the airplane, without having to restrict the airplane to maneuvers that increase the flight time needed to perform a survey. Cycle slip signifies loss of continuous track of the phase of a signal. Minimum-cycle-slip reception is desirable because maintaining constant track of the phase of the carrier signal from each available GPS satellite is necessary for surveying to centimeter or subcentimeter precision. Even a loss of signal for as short a time as a nanosecond can cause cycle slip. Cycle slips degrade the quality and precision of survey data acquired during a flight. The two principal causes of cycle slip are weakness of signals and multipath propagation. Heretofore, it has been standard practice to mount a GPS antenna rigidly on top of an airplane, and the radiation pattern of the antenna is typically hemispherical, so that all GPS satellites above the horizon are viewed by the antenna during level flight. When the airplane must be banked for a turn or other maneuver, the reception hemisphere becomes correspondingly tilted; hence, the antenna no longer views satellites that may still be above the Earth horizon but are now below the equatorial plane of the tilted reception hemisphere. Moreover, part of the reception hemisphere (typically, on the inside of a turn) becomes pointed toward ground, with a consequent increase in received noise and, therefore, degradation of GPS measurements. To minimize the likelihood of loss of signal and cycle slip, bank angles of remote-sensing survey airplanes have generally been limited to 10 or less, resulting in skidding or slipping uncoordinated turns. An airplane must be banked in order to make a coordinated turn. For small-radius, short-time coordinated turns, it is necessary to employ banks as steep as 45 , and turns involving such banks are times and for confining airplanes as closely as possible to areas to be surveyed. The idea underlying the design is that if the antenna can be kept properly aimed, then the incidence of cycle slips caused by loss or weakness of signals can be minimized. The system includes an articulating GPS antenna and associated electronic circuitry mounted under a radome atop an airplane. The electronic circuitry includes a microprocessor-based interface-circuit-and-data-translation module. The system receives data on the current attitude of the airplane from the inertial navigation system of the airplane. The microprocessor decodes the attitude data and uses them to compute commands for the GPS-antenna-articulating mechanism to tilt the antenna, relative to the airplane, in opposition to the roll or bank of the airplane to keep the antenna pointed toward the zenith. The system was tested aboard the hurricane- hunting airplane of the National Oceanic and Atmospheric Administration (NOAA) [see figure] during an 11-hour flight to observe the landfall of Hurricane Bret in late summer of 1999. No bank-angle restrictions were imposed during the flight. Post-flight analysis of the GPS trajectory data revealed that no cycle slip had occurred.considered normal maneuvers. These steep banks are highly desirable for minimizing flight

Wright, C. Wayne↗

Similar but Different: Structural and Spectroscopic Characterization of Series of Neodymium, Europium, Americium, and Curium Coordination Complexes

Series of curium, americium, europium, and neodymium complexes with five different polyoxometalate (POM) ligands were structurally and spectroscopically characterized: Na x Cs y H z [M(XW 11 O 39 ) 2 ]· n H 2 O, where M = Nd 3+ , Eu 3+ , Am 3+ , or Cm 3+ and X = B 3+ , Ga 3+ , Si 4+ , Ge 4+ , or P 5+ . This first “serial approach” on transplutonium chemistry was allowed by minimizing the amount of f-element needed per synthesis down to ∼10 μg. This offers a unique opportunity to contrast structural and spectroscopic properties of trivalent actinide with those of lanthanide compounds under identical conditions. The results showcase that although actinide(III) and lanthanide(III) can make isostructural complexes, their solid-state coordination chemistries deviate significantly. The curium and americium compounds were found to be more uniform than their europium and neodymium counterparts, respectively. The particular symmetry of the Cm-POMs also enables the observation of rarely seen emission bands, which hints at vibronic coupling or new emissive pathways. Additionally, the Cm-POM and Eu-POM complexes were characterized via steady-state and time-resolved excitation and emission spectroscopy in solutions containing five different counterions (Li + , Na + , K + , Rb + , or Cs + ), representing 50 combinations of alkali/[M III (XW 11 ) 2 ] n − complexes. The Cm-POMs respond to the alkali counterions by improving symmetry from Li + to Cs + , while the Eu-POMs do the opposite. The luminescence lifetimes of the Cm-POMs also depart from the ideal Kimura equation. Finally, this study provides a rare, and perhaps the most comprehensive, experimental data set comparing heavy actinides and lanthanides via single crystal XRD plus, solution-state, solid-state, and time-resolved emission spectroscopy and demonstrates that lanthanides are only a coarse approximation for actinide elements.

chemical structure↗

General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate

Given the growing emphasis on energy efficiency, environmental sustainability, and agricultural demand, there’s a pressing need for decentralized and scalable ammonia production. Converting nitrate ions electrochemically, which are commonly found in industrial wastewater and polluted groundwater, into ammonia offers a viable approach for both wastewater treatment and ammonia production yet limited by low producibility and scalability. Here we report a versatile and scalable solution-phase synthesis of high-entropy single-atom nanocages (HESA NCs) in which Fe and other five metals-Co, Cu, Zn, Cd, and In-are isolated via cyano-bridges and coordinated with C and N, respectively. Incorporating and isolating the five metals into the matrix of Fe resulted in Fe-C5 active sites with a minimized symmetry of lattice as well as facilitated water dissociation and thus hydrogenation process. As a result, the Fe-HESA NCs exhibited a high selectivity toward NH3 from the electrocatalytic reduction of nitrate with a Faradaic efficiency of 93.4% while maintaining a high yield rate of 81.4 m h -1 mg -1 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Algorithm For Hypersonic Flow In Chemical Equilibrium

Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

Palmer, Grant↗

Crossed, Small-Deflection Energy Analyzer for Wind/Temperature Spectrometer

Determination of neutral winds and ion drifts in low-Earth-orbit missions requires measurements of the angular and energy distributions of the flux of neutrals and ions entering the satellite from the ram direction. The magnitude and direction of the neutral-wind (or ion-drift) determine the location of the maximum in the angular distribution of the flux. Knowledge of the angle of maximum flux with respect to satellite coordinates (pointing) is essential to determine the wind (or ion-drift) vector. The crossed Small-Deflection Energy Analyzer (SDEA) spectrometer (see Figure 1) occupies minimal volume and consumes minimal power. Designed for upper atmosphere/ionosphere investigations at Earth altitudes above 100 km, the spectrometer operates by detecting the angular and energy distributions of neutral atoms/molecules and ions in two mutually perpendicular planes. In this configuration, the two detection planes actually cross at the spectrometer center. It is possible to merge two SDEAs so they share a common optical axis and alternate measurements between two perpendicular planes, and reduce the number of ion sources from two to one. This minimizes the volume and footprint significantly and reduces the ion source power by a factor of two. The area of the entrance aperture affects the number of ions detected/second and also determines the energy resolution. Thermionic emitters require heater power of about 100 mW to produce 1 mA of electron beam current. Typically, electron energy is about 100 eV and requires a 100-V supply for electron acceleration to supply an additional 100 mW of power. Thus, ion source power is at most 200 mW. If two ion sources were to be used, the ion source power would be, at most, 400 mW. Detector power, deflection voltage power, and microcontroller and other functions require less than 150 mW. A WTS (wind/ temperature spectrometer) with two separate optical axes would consume about 650 mW, while the crossed SDEA described here consumes about 350 mW. The entrance aperture has a diameter of 0.004 in. (0.10 mm) to provide the required energy resolution between 0.05 and 0.15. This design (see Figure 2) provides a WTS occupying a volume less than 40 cm(sup 3), on a footprint of diameter about 1.5 in. (38 mm). The Crossed SDEA offers many advantages in the measurements of neutral wind and ion drifts in the Earth's thermosphere. As such, it will be useful in future commercial satellites dedicated to monitoring the ionosphere with a view to improving the integrity and predictability of GPS operations.

Herrero, Federico A.↗

Towards the Development of a Global, Satellite-based, Terrestrial Snow Mission Planning Tool

A global, satellite-based, terrestrial snow mission planning tool is proposed to help inform experimental mission design with relevance to snow depth and snow water equivalent (SWE). The idea leverages the capabilities of NASAs Land Information System (LIS) and the Tradespace Analysis Tool for Constellations (TAT C) to harness the information content of Earth science mission data across a suite of hypothetical sensor designs, orbital configurations, data assimilation algorithms, and optimization and uncertainty techniques, including cost estimates and risk assessments of each hypothetical orbital configuration.One objective the proposed observing system simulation experiment (OSSE) is to assess the complementary or perhaps contradictory information content derived from the simultaneous collection of passive microwave (radiometer), active microwave (radar), and LIDAR observations from space-based platforms. The integrated system will enable a true end-to-end OSSE that can help quantify the value of observations based on their utility towards both scientific research and applications as well as to better guide future mission design. Science and mission planning questions addressed as part of this concept include:1. What observational records are needed (in space and time) to maximize terrestrial snow experimental utility?2. How might observations be coordinated (in space and time) to maximize utility? 3. What is the additional utility associated with an additional observation?4. How can future mission costs being minimized while ensuring Science requirements are fulfilled?

Mission Design↗

Scanning structural mapping at the Life Science X-ray Scattering Beamline

This work describes the instrumentation and software for microbeam scattering and structural mapping at the Life Science X-ray Scattering (LiX) beamline at NSLS-II. Using a two-stage focusing scheme, an adjustable beam size between a few micrometres and a fraction of a millimetre is produced at the sample position. Scattering data at small and wide angles are collected simultaneously on multiple Pilatus detectors. A recent addition of an in-vacuum Pilatus 900k detector, with the detector modules arranged in a C-shaped configuration, has improved the azimuthal angle coverage in the wide-angle data. As an option, fluorescence data can be collected simultaneously. Fly scans have been implemented to minimize the time interval between scattering patterns and to avoid unnecessary radiation damage to the sample. For weakly scattering samples, an in-vacuum sample environment has been developed here to minimize background scattering. Data processing for these measurements is highly sample-specific. To establish a generalized data process workflow, first the data are reduced to reciprocal coordinates at the time of data collection. The users can then quantify features of their choosing from these intermediate data and construct structural maps. As examples, results from in-vacuum mapping of onion epidermal cell walls and 2D tomographic sectioning of an intact poplar stem are presented.

36 MATERIALS SCIENCE↗

Battery Degradation Modeling in Hybrid Power Plants: An Island System Unit Commitment Study: Preprint

As hybrid power plants (HPPs), such as photovoltaic (PV) and battery combinations, become increasingly important in power systems with high renewable energy penetration to address PV variability and ensure grid stability. This paper focuses on the urgent need to model the coordination between PV and battery systems in HPPs while accounting for battery degradation. We present a generation scheduling model that explicitly incorporates PV-battery hybridization in the unit commitment problem. Moreover, the cost function of the HPP scheduling problem endogenously considers battery degradation with adjustable weights to strike a balance between minimizing production costs and prolonging battery life, particularly when providing energy arbitrage and ancillary services. Using a realistic island system simulation, we demonstrate that accounting for battery degradation in the scheduling problem can significantly extend battery life with only minor additional production costs.

battery degradation↗

Evaluating the Curtailment Risk of Non-Firm Utility-Scale Solar Photovoltaic Plants under a Novel Last-In First-Out Principle of Access Interconnection Agreement

With the increasing share of distributed energy resources on the electric grid, utility companies are facing significant decisions about infrastructure upgrades. An alternative to extensive and capital-intensive upgrades is to offer non-firm interconnection opportunities to distributed generators, via a coordinated operation of utility scale resources. This paper introduces a novel flexible interconnection option based on the last-in, first-out principles of access aimed at minimizing the unnecessary non-firm generation energy curtailment by balancing access rights and contribution to thermal overloads. Although we focus on solar photovoltaic (PV) plants in this work, the introduced flexible interconnection option applies to any distributed generation technology. The curtailment risk of individual non-firm PV units is evaluated across a range of PV penetration levels in a yearlong quasi-static time-series simulation on a real-world feeder. The results show the importance of the size of the curtailment zone in the curtailment risk distribution among flexible generation units as well as that of the “access right” defined by the order in which PV units connect to the grid. Case study results reveal that, with a proper selection of curtailment radius, utilities can reduce the total curtailment of flexible PV resources by up to more than 45%. Findings show that non-firm PV generators can effectively avoid all thermal limit-related upgrade costs.

14 SOLAR ENERGY↗

The Application of Advanced Cultivation Techniques in the Long Term Maintenance of Space Flight Plant Biological Systems

The development of the International Space Station (ISS) presents extensive opportunities for the implementation of long duration space life sciences studies. Continued attention has been placed in the development of plant growth chamber facilities capable of supporting the cultivation of plants in space flight microgravity conditions. The success of these facilities is largely dependent on their capacity to support the various growth requirements of test plant species. The cultivation requirements for higher plant species are generally complex, requiring specific levels of illumination, temperature, humidity, water, nutrients, and gas composition in order to achieve normal physiological growth and development. The supply of water, nutrients, and oxygen to the plant root system is a factor, which has proven to be particularly challenging in a microgravity space flight environment. The resolution of this issue is particularly important for the more intensive crop cultivation of plants envisaged in Nasa's advanced life support initiative. BioServe Space Technologies is a NASA, Research Partnership Center (RPC) at the University of Colorado, Boulder. BioServe has designed and operated various space flight plant habitat systems, and placed specific emphasis on the development and enhanced performance of subsystem components such as water and nutrient delivery, illumination, gas exchange and atmosphere control, temperature and humidity control. The further development and application of these subsystems to next generation habitats is of significant benefit and contribution towards the development of both the Space Plant biology and the Advanced Life Support Programs. The cooperative agreement between NASA Ames Research center and BioServe was established to support the further implementation of advanced cultivation techniques and protocols to plant habitat systems being coordinated at NASA Ames Research Center. Emphasis was placed on the implementation of passive-based water and nutrient support systems and techniques, which can be used to minimize demands on power, mass, and operational complexity in space flight studies. This effort has direct application to the development of next-generation space flight plant chambers such as the Plant Research Unit (PRU). Work was also directed at the development of in-flight plant preservation techniques and protocols consistent with the interest in applying recent developments in gene chip micro array technologies. Cultivation technologies and protocols were evaluated in a 55 day space flight plant growth study, conducted on the ISS, mission 9A (10/7/02 - 12/7/02).

Heyenga, A. G.↗

Catalytic, Spectroscopic, and Theoretical Studies of Fe 4 S 4 -Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Iron–sulfur clusters play essential roles in biological systems, and thus synthetic [Fe 4 S 4 ] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe 4 S 4 ] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO 2 reduction catalyst. Here, in this work, we demonstrate that incorporating these [Fe 4 S 4 ] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe 4 S 4 -based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO 2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn–H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe 4 S 4 ] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗