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At least 217 records · Page 12

Variable response load limiting device

An energy absorbing device used as a load limiting member in a structure to control its response to applied loads is described. It functions by utilizing a spool assembly having flanged ends and an interior cavity of sufficiently large diameter to cause it to deform plastically at a prescribed load. In application, the spool is utilized as a pivot point for the legs of an airplane seat. When properly designed and integrated into the seat arrangement the spool will twist about its axis, deforming plastically when the impact load exceeds the spool yield value. Through this deformation, the spool absorbs the kinetic energy of the movement of the seat at a substantially constant rate, thereby controlling the level of loads transmitted to the seat occupant. By proper sizing and collection of materials, it is possible to control load response in a predictable manner.

Mcsmith, Dwight D.↗

Low-spin cobalt(ii) redox shuttle by isocyanide coordination

Coordination of the strong-field ligand 2,6-dimethylphenyl isocyanide (DMP-CN) to the Co(PY5Me 2 ) framework, where PY5Me 2 represents the pentadentate ligand 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine, has resulted in a new low-spin Co(II) complex with a relatively low reorganization energy and fast electron-transfer kinetics compared to the prototypical cobalt tris-bipyridine redox shuttle, [Co(bpy) 3 ] 3+/2+ , where bpy represents 2,2'-bipyridine. Despite nearly 160 mV reduced regeneration driving force, the [Co(PY5Me 2 )(DMP-CN)]3+/2+ redox shuttle displayed an increased regeneration efficiency relative to [Co(bpy)3] 3+/2+ , however recombination losses hinder the performance as evidenced by a reduced recombination resistance. Finally, future directions point to low-spin Co(II) redox shuttles with more negative redox potentials to be paired with a dye or dye mixture that absorbs into the near infrared region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Impact of Buoyancy and Flame Structure on Soot, Radiation and NOx Emissions from a Turbulent Diffusion Flame

It is hypothesized that the spatial structure of a turbulent diffusion flame plays an important role in determining the emissions of radiative energy, soot and NO, from a combustor. This structure, manifested in the two point statistics, is influenced by buoyancy. Radiation, soot and NOx emissions are the cumulative result of processes that occur throughout a flame. For example, radiation fluxes along a line of sight can be found from summing up the contributions from sources in individual pockets of hot soot that emit, and from sinks in cold soot that absorb. Soot and NOx are both the results of slow chemistry and are not equilibrium products. The time that is available for production and burnout is crucial in determining the eventual emissions of these pollutants. Turbulence models generally rely on a single point closure of the appropriate time averaged equations. Hence, spatial information is lost and needs to be modeled using solution variables such as turbulence kinetic energy and dissipation rate, often with the assumption of isotropy. However, buoyancy can affect the physical structure of turbulent flames and can change the spatial extent of soot bearing regions. Theoretical comparisons with models are best done in the limit of infinite Froude number because the inclusion of buoyancy in flow models introduces significant uncertainties. Hence, LII measurements of soot, measurements of radiation fluxes from soot, Particle Imaging Velocimetry (PIV) of the flow field and measurements of post flame NOX will be carried out on the NASA Lewis 2.2 sec drop tower and eventually on the parabolic flight aircraft. The drop rig will be a modified version of a unit that has been successfully used at Lewis in the past.

Kennedy, I. M.↗

Multiwavelength Observations of 2HWC J1928+177: Dark Accelerator or New TeV Gamma-Ray Binary?

2HWC J1928+177 is a Galactic TeV gamma-ray source detected by the High Altitude Water Cherenkov (HAWC) Observatory up to ~56 TeV. The HAWC source, later confirmed by the High Energy Stereoscopic System, still remains unidentified as a dark accelerator since there is no apparent supernova remnant or pulsar wind nebula detected in the lower-energy bands. The radio pulsar PSR J1928+1746, coinciding with the HAWC source position, has no X-ray counterpart. In this work, our SED modeling shows that inverse Compton scattering in the putative pulsar wind nebula can account for the TeV emission only if the unseen nebula is extended beyond $r\sim 4^{\prime} $. Alternatively, TeV gamma-rays may be produced by hadronic interactions between relativistic protons from an undetected supernova remnant associated with the radio pulsar and a nearby molecular cloud G52.9+0.1. NuSTAR and Chandra observations detected a variable X-ray point source within the HAWC error circle, potentially associated with a bright infrared (IR) source. The X-ray spectra can be fitted with an absorbed power-law model with N H = (9 ± 3) × 10 22 cm –2 and Γ X = 1.6 ± 0.3 and exhibit long-term X-ray flux variability over the last decade. If the X-ray source, possibly associated with the IR source (likely an O star), is the counterpart of the HAWC source, it may be a new TeV gamma-ray binary powered by collisions between the pulsar wind and stellar wind. Follow-up X-ray observations are warranted to search for diffuse X-ray emission and determine the nature of the HAWC source.

79 ASTRONOMY AND ASTROPHYSICS↗

IRAS observations of cometary dust

It is pointed out that solid material present in the coma and tail of a comet is revealed by the scattering of sunlight and thermal emission of absorbed solar radiation. The large beam size and low background of the cold Infrared Astronomy Satellite (IRAS) telescope make it extremely well suited to the measurement of faint diffuse thermal emission from solid grains associated with comets. The IRAS project was conducted jointly by the Netherlands, the United Kingdom, and the U.S. Its basic objective involved a survey of the sky in four wavelength regions centered on 12, 25, 60, and 100 microns. The present paper is mainly concerned with IRAS observations of the coma-nucleus regions as defined by the maximum in the intensity distribution. Attention is given to circumstances of comet observations, dust production rates, and a discussion of the results.

Walker, R. G.↗

Reactionless gimbal actuator for precision pointing of large payloads

A novel actuator for application to precision pointing gimbal systems is described. The new actuator, dubbed the Reactuator, is capable of large output torques for payload pointing while minimizing reaction torques that can excite gimbal support structure. The Reactuator is able to approach reactionless operation by using an integral wheel to absorb the reaction torques. The advantages that result are described through analysis and simulation examples. Methods for designing control algorithms for the Reactuator are discussed and the results of preliminary breadboard tests are presented.

Laskin, R. A.↗

PSR J2022 plus 3842: An Energetic Radio and X-Ray Pulsar Associated with SNR G76.9 plus 1.0

We present Chandra X-ray Observatory, Robert C. Byrd Green Bank Radio Telescope (GBT), and Rossi X-ray Timing Explorer (RXTE) observations directed toward the radio supernova remnant (SNR) G76.9+1.0. The Chandra investigation reveals a hard, unresolved X-ray source coincident with the midpoint of the double-lobed radio morphology and surrounded by faint, compact X-ray nebulosity. These features suggest that an energetic neutron star is powering a pulsar wind nebula (PWN) seen in synchrotron emission. Indeed, the spatial relationship of the X-ray and radio emissions is remarkably similar to the extended emission around the Vela pulsar. A follow-up pulsation search with the GBT uncovered a highly-dispersed (DM = 427 +/- 1 pc/cu cm) and highly-scattered pulsar with a period of 24 ms. Its subsequently measured spin-down rate implies a characteristic age T(sub c) = 8.9 kyr, making PSR J2022+3842 the most rapidly rotating young radio pulsar known. With a spin-down luminosity E = 1.2 x 10(exp 38) erg/s, it is the second-most energetic Galactic pulsar known, after the Crab pulsar. The 24-ms pulsations have also been detected in the RXTE observation; the combined Chandra and RXTE spectral fit suggests that the Chandra point-source emission is virtually 100% pulsed. The 2-16 keV spectrum of the narrow (0.06 cycles FWHM) pulse is well-fitted by an absorbed power-law model with column density N(sub H) = (1.7 +/- 0.5) x 10(exp 22)/sq cm and photon index Gamma = 1.0 +/- 0.2, strongly suggestive of magnetospheric emission. For an assumed distance of 10 kpc, the 2-10 keV luminosity of L(sub X) = 6.9 x 10(exp 33) erg/s suggests one of the lowest known X-ray conversion efficiencies L(sub X)/ E = 5.8 x 10(exp -5), similar to that of the Vela pulsar. Finally, the PWN around PSR J2022+3842 revealed by Chandra is also underluminous, with F(sub PWN)/ F(sub PSR) < or approx.1 in the 2-10 keV band, a further surprise given the pulsar's high spin-down luminosity.

Arzoumanian, Z.↗

Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System

TDA developed and demonstrated a highly efficient pre-combustion carbon capture system. The overall objective of this work was to develop a new sorbent-based pre-combustion carbon capture technology for Integrated Gasification Combined Cycle (IGCC) power plants. In this project our goal was to demonstrate the techno-economic viability of the new technology by 1) demonstrating it in large-scale slipstream tests, and 2) carrying out a high fidelity engineering and cost analysis. TDA’s process used an advanced physical adsorbent that selectively removes CO 2 from coal-derived synthesis gas above the dew point of the gas at temperatures as high as 300°C. The sorbent consists of a mesoporous carbon whose surface was grafted with functional groups that remove CO 2 via a well-known acid-base interaction. As documented in bench-scale experiments and field tests with actual coal gas, the sorbent achieved a very high capacity for CO 2 at temperatures as high as 300°C. The sorbent bound CO 2 more strongly than common physical adsorbents, providing the chemical potential needed for the high temperature operation. However, because CO 2 does not form a true covalent bond with the surface sites (as is the case with chemical absorbents), the sorbent regeneration could be carried out with only a very small energy input. The heat input to regenerate our sorbent was only 4.9 kcal per mol of CO 2 , which is much lower than that for chemical absorbents (e.g., 29.9 kcal/mol CO 2 for sodium carbonate) and was similar to the requirements of physical solvents (e.g., 4 kcal/mol CO 2 for Selexol TM ). Because the sorbent operates above the dew point of the synthesis gas (unlike the Selexol TM process), a higher power cycle efficiency can be achieved. With previous DOE/NETL funding (Contract No. DE-FE-0000469), we demonstrated the techno-economic viability of the technology in bench-scale tests and slipstream demonstrations at the National Carbon Capture Center (NCCC), Wilsonville, Alabama and Wabash River IGCC plant in Terra Haute, Indiana. We demonstrated a stable working CO 2 capacity for over 11,650 cycles with simulated synthesis gas. We also evaluated its performance with actual synthesis gas in two test campaigns at the Wabash River IGCC Plant, Terre Haute, IN and the National Carbon Capture Center (NCCC), Wilsonville, AL. The slipstream tests clearly showed that the actual coal gas constituents and potential contaminants (e.g. trace metals, halides, tars) had no effect on the sorbent’s ability to remove CO 2 (the same sorbent beds were used in both field tests with no sign of deactivation for 2,000 cycles with over 26,750 SCF of gas treated). As expected, due to the high temperature CO 2 removal capability and low energy needed to regenerate the sorbent, the power cycle efficiency with our process was greater than 34% on a higher heating value (HHV) basis; in comparison, the same IGCC plant equipped with the Selexol TM solvent for carbon capture can only achieve 31.4% HHV efficiency. The capital cost for an IGCC system with TDA’s process is estimated as $2,417/kW e , which is 12% lower than that of the IGCC/ Selexol TM process. The levelized cost for electricity including the transport, storage and monitoring (TS&M) cost for CO 2 was calculated as $\$ $92.9/MWh (lowest reported to our knowledge), which is much better than the $105.2/MWh estimated for the IGCC/ Selexol TM process. In this project (DE-FE0013105), TDA Research, in collaboration with our partners Gas Technology Institute (GTI), Illinois Clean Coal Institute (ICCI), University of California, Irvine (UCI), University of Alberta (UOA), Siemens, NCCC and Sinopec advanced the technical maturity of the technology; scaling it up by a factor of 100. We optimized the reactor design using computational fluid dynamics (CFD); using adsorption modeling we improved the pressure swing adsorption (PSA) cycle sequence. We carried out two field test campaigns with a fully-equipped 0.1 MW e prototype unit (for a total of 844 hours) using actual synthesis gas to prove the viability of the new technology. A successful 30 day (707 hrs) evaluation was completed at NCCC under air blown gasification conditions. We demonstrated 97.3% carbon capture at 1,500 SLPM, 93% carbon capture at 1,800 SLPM, and 90% carbon capture at 2,100 SLPM in the NCCC tests. We also demonstrated the system for 137 hours at a Sinopec petrochemical plant under oxygen blown gasification, demonstrating 86% carbon capture at 2,660 SLPM. In collaboration with University of California, Irvine (UCI), we completed a techno-economic analysis (TEA) for TDA’s warm gas cleanup technology integrated to IGCC power plant. The net plant efficiencies (on a coal HHV basis) for the warm gas cleanup cases were estimated to be 34.0% for E-GasTM gasifier, 34.4% for GE gasifier, 33.4 for the Shell gasifier and 34.2 for the TRIG TM gasifier (Cases 2, 4, 6 and 8 in this study) with a catalytic combustor for CO 2 purification, which are significantly higher than those for the Cold Gas Case, or an increase of as much as 12% in the heat rate for Case 2, 6% for Case 4, 9% for Case 6, and 9% for Case 8. The 1st year cost of electricity with the transport, storage and monitoring (TS&M) costs for the CO 2 included was $\$ $129.2/MWh for the E-GasTM gasifier Warm Gas Cleanup Case, $\$ $131.9/MWh for the GE gasifier Warm Gas Cleanup Case, $\$ $146.8/MWh for the Shell Gasifier Warm Gas Cleanup Case, and $\$ $129.9/MWh for the TRIG TM gasifier Warm Gas Cleanup Case. For comparison, the costs for the baseline Cold Gas CO 2 removal with Selexol for the different gasifiers were: $\$ $146.6/MWh for the E-Gas TM gasifier, $\$ $142.2/MWh for the GE gasifier, $\$ $159.0/MWh for the Shell gasifier and $\$ $144.3/MWh for the TRIG TM gasifier. In summary, the costs for our system were 7 to 12% lower than the corresponding Cold Gas Cleanup cases. The results of this techno-economic analysis suggested that TDA’s high temperature PSA-based Warm Gas Clean-up Technology can make a substantial improvement in the IGCC plant thermal performance for achieving near zero CO 2 emissions for E-Gas TM , GE, Shell and TRIG TM gasifier based IGCC power plants. The capital expenses were estimated to be lower than that of Selexol’s™. Taken together, the higher net plant efficiency and lower capital and operating costs resulted in substantial reduction in the cost of carbon capture for the IGCC plant equipped with TDA’s high temperature PSA-based carbon capture system. Finally, in collaboration with Gas Technology Institute (GTI) we completed the environmental health and safety assessment for TDA’s warm gas carbon capture technology.

01 COAL, LIGNITE, AND PEAT↗

Tree-based solvers for adaptive mesh refinement code $\scriptsize{FLASH}$ – IV. An X-ray radiation scheme to couple discrete and diffuse X-ray emission sources to the thermochemistry of the interstellar medium

X-ray radiation, in particular radiation between 0.1 and 10 keV, is evident from both point-like sources, such as compact objects and T-Tauri young stellar objects, and extended emission from hot, cooling gas, such as in supernova remnants. The X-ray radiation is absorbed by nearby gas, providing a source of both heating and ionization. While protoplanetary chemistry models now often include X-ray emission from the central young stellar object, simulations of star-forming regions have yet to include X-ray emission coupled to the chemo-dynamical evolution of the gas. We present an extension of the $\scriptsize{TREERAY}$ reverse ray trace algorithm implemented in the flash magnetohydrodynamic code which enables the inclusion of X-ray radiation from 0.1 keV < E γ < 100 keV, dubbed $\scriptsize{XRAYTHESPOT}$. $\scriptsize{XRAYTHESPOT}$ allows for the use of an arbitrary number of bins, minimum and maximum energies, and both temperature-independent and temperature-dependent user-defined cross-sections, along with the ability to include both point and extended diffuse emission and is coupled to the thermochemical evolution. We demonstrate the method with several multibin benchmarks testing the radiation transfer solution and coupling to the thermochemistry. Finally, we show two example star formation science cases for this module: X-ray emission from protostellar accretion irradiating an accretion disc and simulations of molecular clouds with active chemistry, radiation pressure, and protostellar radiation feedback from infrared to X-ray radiation.

79 ASTRONOMY AND ASTROPHYSICS↗

Cloud Imagers Offer New Details on Earth's Health

A stunning red sunset or purple sunrise is an aesthetic treat with a scientific explanation: The colors are a direct result of the absorption or reflectance of solar radiation by atmospheric aerosols, minute particles (either solid or liquid) in the Earth s atmosphere that occur both naturally and because of human activity. At the beginning or end of the day, the Sun s rays travel farther through the atmosphere to reach an observer s eyes and more green and yellow light is scattered, making the Sun appear red. Sunset and sunrise are especially colorful when the concentration of atmospheric particles is high. This ability of aerosols to absorb and reflect sunlight is not just pretty; it also determines the amount of radiation and heat that reaches the Earth s surface, and can profoundly affect climate. In the atmosphere, aerosols are also important as nuclei for the condensation of water droplets and ice crystals. Clouds with fewer aerosols cannot form as many water droplets (called cloud particles), and consequently, do not scatter light well. In this case, more sunlight reaches the Earth s surface. When aerosol levels in clouds are high, however, more nucleation points can form small liquid water droplets. These smaller cloud particles can reflect up to 90 percent of visible radiation to space, keeping the heat from ever reaching Earth s surface. The tendency for these particles to absorb or reflect the Sun s energy - called extinction by astronomers - depends on a number of factors, including chemical composition and the humidity and temperature in the surrounding air; because cloud particles are so small, they are affected quickly by minute changes in the atmosphere. Because of this sensitivity, atmospheric scientists study cloud particles to anticipate patterns and shifts in climate. Until recently, NASA s study of atmospheric aerosols and cloud particles has been focused primarily on satellite images, which, while granting large-scale atmospheric analysis, limited scientists ability to acquire detailed information about individual particles. Now, experiments with specialized equipment can be flown on standard jets, making it possible for researchers to monitor and more accurately anticipate changes in Earth s atmosphere and weather patterns.

Source record↗

The response of fluoroscopic image intensifier-TV systems

Three different types of X-ray fluoroscopic TV chains were investigated: two standard clinical units, one with a vidicon camera tube, the other with a plumbicon camera tube; and the third was a large flat-screen unit. In each an X-ray beam generated at 100 kVp was passed through 10 cm of H2O before aluminum absorbers of varying thickness were introduced. Five video recordings were made at each absorber thickness. The video image was digitized directly from the disk recording and quantized into 128 gray levels. The five recordings were averaged on a point-to-point basis, and the central 900 averaged points were again averaged to yield a value for the gray level assigned to each particular image. This 30 by 30 matrix of points corresponds to input screen areas of 29, 8.2, and 3.6 sq cm for the three units investigated.

Baily, N. A.↗

Instrumented impact and residual tensile strength testing of eight-ply carbon eopoxy specimens

Instrumented drop weight impact testing was utilized to examine a puncture-type impact on thin carbon-epoxy coupons. Four different material systems with various eight-ply lay-up configurations were tested. Specimens were placed over a 10.3-mm diameter hole and impacted with a smaller tup (4.2-mm diameter) than those used in previous studies. Force-time plots as well as data on absorbed energy and residual tensile strength were gathered and examined. It was found that a critical impact energy level existed for each material tested, at which point tensile strength began to rapidly decrease with increasing impact energy.

Nettles, A. T.↗

Climatic implications of the simultaneous presence of CO2 and H2O in the Martian regolith

The current paradigm for quasi-periodic climate change on Mars holds that perhaps a few hundred millibars of CO2 are available for exchange between the atmosphere and regolith, and that a vast majority of that CO2 is presently absorbed into the regolith. The CO2 is partitioned between the regolith and atmosphere according to an equilibrium adsorptive relationship. If the atmospheric pressure exceeds the frost point at or near the poles, then quasi-permanent polar caps form and buffer the atmospheric pressure. This model was developed based upon laboratory studies of CO2 adsorption where no other adsorbates are present. We will conduct laboratory measurements of the simultaneous adsorption of H2O and CO2 under Mars-like conditions, and develop numerical expressions for use in climate modeling based upon our results.

Zent, A. P.↗

An Impact Triggered Runaway Greenhouse on Mars

When a planet is in radiative equilibrium, the incoming solar flux balances the outgoing longwave flux. If something were to perturb the system slightly, say the incoming solar flux increased, the planet would respond by radiating at a higher surface temperature. Since any radiation that comes in must go out, if the incoming is increased, the outgoing must also increase, and this increase manifests itself as a warmer equilibrium temperature. The increase in solar flux would correspond to an increase in temperature, which would increase the amount of water vapor in the atmosphere due to increased evaporation. Since water vapor is a greenhouse gas, it would absorb more radiation in the atmosphere leading to a yet warmer equilibrium temperature. The planet would reach radiative equilibrium at this new temperature. There exists a point, however, past which this positive feedback leads to a "runaway" situation. In this case, the planet does not simply evaporate a little more water and eventually come to a slightly higher equilibrium temperature. Instead, the planet keeps evaporating more and more water until all of the planet's available liquid and solid water is in the atmosphere. The reason for this is generally understood. If the planet's temperature increases, evaporation of water increases, and the absorption of radiation increases. This increases the temperature and the feedback continues until all water is in the atmosphere. The resulting equilibrium temperature is very high, much higher than the equilibrium temperature of a point with slightly lower solar flux. One can picture that as solar flux increases, planetary temperature also increases until the runaway point where temperature suddenly "jumps" to a higher value, in response to all the available water now residing in the atmosphere. This new equilibrium is called a "runaway greenhouse" and it has been theorized that this is what happened to the planet Venus, where the surface temperature is more than 700 K (427 C).

Segura, T. L.↗

From Planetary Imaging to Enzyme Screening

Based in San Diego, KAIROS Scientific develops molecular biology methods, instrumentation, and computer algorithms to create solutions to challenging problems in the medical and chemical industries. company s pioneering efforts in digital imaging spectroscopy (DIS) enable researchers to obtain spectral and/or time-dependent information for each pixel or group of pixels in a two-dimensional scene. In addition to having Yang s NASA experience at its foundation, KAIROS Scientific was established with the support of many government grants and contracts. Its first was a NASA Small Business Innovation Research (SBIR) grant, from Ames Research Center, to develop HIRIM, a high-resolution imaging microscope embodying both novel hardware and software that can be used to simultaneously acquire hundreds of individual absorbance spectra from microscopic features. Using HIRIM s graphical user interface, MicroDIS, scientists and engineers are presented with a revolutionary new tool which enables them to point to a feature in an image and recall its associated spectrum in real time.

Source record↗

Absorption of Solar Radiation by Clouds: A Second Look at Irradiance Measurements

A decade ago, Stephens and Tsay provided an overview of the subject of absorption of solar radiation by clouds in the earth's atmosphere. They summarized the available evidence that pointed to disagreements between theoretical and observed values of cloud absorption (and reflection). At that time, a theoretician's approach (assuming perfect flux measurements) was adopted to test the model uncertainty under various hypotheses, such as the omitted large drops, excess absorbing aerosols, enhanced water vapor continuum absorption, and cloud inhomogeneity. Since then, several advances in theoretical work have been made, but a satisfactory answer for the discrepancy is still lacking. Now, we offer an experimentalist's approach (focusing on field, not laboratory) to examine the observational uncertainty under numerous field factors, such as the temperature dependence, attitude control, and sampling strategy in the spatial and spectral domain. Examples from recent field campaigns have pointed out that these sources of error may be responsible for the unacceptable level of uncertainty (e.g., as large as 20 W/square m). We give examples of each, discuss their contribution to overall uncertainty in shortwave absorption, and suggest a coordinated approach to their solution.

Tsay, Si-Chee↗

CO 2 Uptake and Stability Enhancement in Vinyltrimethoxysilane‐Treated SBA‐15 Solid Amine‐Based Sorbents

Abstract Silica‐supported amine absorbents, including materials produced by tethering aminosilanes or infusion of poly(ethyleneimine), represent a promising class of materials for CO 2 capture applications, including direct air and point source capture. Various silica surface treatments and functionalization strategies are explored to enhance stability and CO 2 uptake in amine‐based solid sorbent systems. Here, the synthesis and characterization of novel vinyltrimethoxysilane‐treated Santa Barbara Amorphous‐15 (SBA‐15) supports and the corresponding enhancement in CO 2 uptake compared to various SBA‐15‐based control supports are presented. The relationship between CO 2 diffusion and amine efficiency in these systems is explored using a previously reported kinetic model. The synthesized materials are characterized with CO 2 and H 2 O isotherms, diffuse reflectance infrared Fourier transform spectroscopy, 1 H T 1 – T 2 relaxation correlation NMR, and rapid thermal cycling experiments. The novel support materials are shown to enable high amine efficiencies, approaching a fourfold improvement over standard SBA‐15‐supported amines, while simultaneously exhibiting excellent stability when cycled rapidly under humid conditions. As the poly(ethyleneimine) loadings are held constant across the various samples, enhancements in CO 2 uptake are attributed to differences in the way the poly(ethyleneimine) interacts with the support surface.

Vallace, Anthony↗

Molecular Switch Cobalt Redox Shuttle with a Tunable Hexadentate Ligand

Strong-field hexadentate ligands were synthesized and coordinated to cobalt metal centers to result in three new low-spin to low-spin Co(III/II) redox couples. The ligand backbone has been modified with dimethyl amine groups to result in redox potential tuning of the Co(III/II) redox couples from –200 to –430 mV versus Fc +/0 . The redox couples surprisingly undergo a reversible molecular switch rearrangement from five-coordinate Co(II) to six-coordinate Co(III) despite the ligands being hexadentate. The complexes exhibit modestly faster electron self-exchange rate constants of 2.2–4.2 M –1 s –1 compared to the high-spin to low-spin redox couple [Co(bpy) 3 ] 3 + /2 + at 0.27 M –1 s –1 , which is attributed to the change in spin state being somewhat offset by this coordination switching behavior. The complexes were utilized as redox shuttles in dye-sensitized solar cells with the near-IR AP25 + D35 dye system and exhibited improved photocurrents over the [Co(bpy) 3 ] 3 + /2 + redox shuttle (19.8 vs 18.0 mA/cm 2 ). Finally, future directions point toward pairing the low-spin to low-spin Co(II/III) tunable series to dyes with significantly more negative highest occupied molecular orbital potentials that absorb into the near-IR where outer sphere redox shuttles have failed to produce efficient dye regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗