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At least 1,423 records · Page 79

Surface-slip equations for multicomponent nonequilibrium air flow

Equations are presented for the surface-slip (or jump) values of species concentration, pressure, velocity, and temperature in the low-Reynolds number, high-altitude flight regime of a space vehicle. The equations are obtained from closed form solutions of the mass, momentum, and energy flux equations using the Chapman-Enskog velocity distribution function. This function represents a solution of the Boltzmann equation in the Navier-Stokes approximation. The analysis, obtained for nonequilibrium multicomponent air flow, includes the finite-rate surface catalytic recombination and changes in the internal energy during reflection from the surface. Expressions for the various slip quantities were obtained in a form which can be employed in flowfield computations. A consistent set of equations is provided for multicomponent, binary, and single species mixtures. Expression is also provided for the finite-rate, species-concentration boundary condition for a multicomponent mixture in absence of slip.

Gupta, R. N.↗

Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure

Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.

Xu, F.↗

Testing of the Multi-Fluid Evaporator Engineering Development Unit

Hamilton Sundstrand is under contract with the NASA Johnson Space Center to develop a scalable, evaporative heat rejection system called the Multi-Fluid Evaporator (MFE). It is being designed to support the Orion Crew Module and to support future Constellation missions. The MFE would be used from Earth sea level conditions to the vacuum of space. The current Shuttle configuration utilizes an ammonia boiler and flash evaporator system to achieve cooling at all altitudes. The MFE system combines both functions into a single compact package with significant weight reduction and improved freeze-up protection. The heat exchanger core is designed so that radial flow of the evaporant provides increasing surface area to keep the back pressure low. The multiple layer construction of the core allows for efficient scale up to the desired heat rejection rate. The full scale MFE prototype will be constructed with four core sections that, combined with a novel control scheme, manage the risk of freezing the heat exchanger cores. A sub-scale MFE engineering development unit (EDU) has been built, and is identical to one of the four sections of a full scale prototype. The EDU has completed testing at Hamilton Sundstrand. The overall test objective was to determine the thermal performance of the EDU. The first set of tests simulated how each of the four sections of the prototype would perform by varying the chamber pressure, evaporant flow rate, coolant flow rate and coolant temperature. A second set of tests was conducted with an outlet steam header in place to verify that the outlet steam orifices prevent freeze-up in the core while also allowing the desired thermal turn-down ratio. This paper discusses the EDU tests and results.

Quinn, Gregory↗

Integrated Locomotor Function Tests for Countermeasure Evaluation

Following spaceflight crewmembers experience locomotor dysfunction due to inflight adaptive alterations in sensorimotor function. Countermeasures designed to mitigate these postflight gait alterations need to be assessed with a new generation of tests that evaluate the interaction of various sensorimotor sub-systems central to locomotor control. The goal of the present study was to develop new functional tests of locomotor control that could be used to test the efficacy of countermeasures. These tests were designed to simultaneously examine the function of multiple sensorimotor systems underlying the control of locomotion and be operationally relevant to the astronaut population. Traditionally, gaze stabilization has been studied almost exclusively in seated subjects performing target acquisition tasks requiring only the involvement of coordinated eye-head movements. However, activities like walking involve full-body movement and require coordination between lower limbs and the eye-head-trunk complex to achieve stabilized gaze during locomotion. Therefore the first goal of this study was to determine how the multiple, interdependent, full-body sensorimotor gaze stabilization subsystems are functionally coordinated during locomotion. In an earlier study we investigated how alteration in gaze tasking changes full-body locomotor control strategies. Subjects walked on a treadmill and either focused on a central point target or read numeral characters. We measured: temporal parameters of gait, full body sagittal plane segmental kinematics of the head, trunk, thigh, shank and foot, accelerations along the vertical axis at the head and the shank, and the vertical forces acting on the support surface. In comparison to the point target fixation condition, the results of the number reading task showed that compensatory head pitch movements increased, peak head acceleration was reduced and knee flexion at heel-strike was increased. In a more recent study we investigated the adaptive remodeling of the full-body gaze control systems following exposure to visual-vestibular conflict. Subjects walked on a treadmill before and after a 30- minute exposure to 0.5X minifying during which self-generated sinusoidal vertical head rotations were performed while seated. Following exposure to visual-vestibular conflict subjects showed a restriction in compensatory head movements, increased knee and ankle flexion after heel-strike and a decrease in the rate of body loading during the rapid weight transfer phase after the heel strike event. Taken together, results from both studies provide evidence that the full body contributes to gaze stabilization during locomotion, and that different functional elements are responsive to changes in visual task constraints and are subject to adaptive alterations following exposure to visual-vestibular conflict. This information provides the basis for the design of a new generation of integrative tests that incorporate the evaluation of multiple neural control systems relevant to astronaut operational performance.

Bloomberg, J. J.↗

Analysis of Plastic Flow Instability During Superplastic Deformation of the Zn-Al Eutectoid Alloy Modified with 2 wt.% Cu

The aim of this work is to analyze the plastic flow instability in Zn-21Al-2Cu alloy deformed under 10{sup −3} s{sup −1} and 513 K, which are optimum conditions for inducing superplastic behavior in this alloy. An evaluation using the Hart and Wilkinson–Caceres criteria showed that the limited stability of plastic flow observed in this alloy is related to low values of the strain-rate sensitivity index (m) and the strain-hardening coefficient (γ), combined with the tendency of these parameters to decrease depending on true strain (ε). The reduction in m and γ values could be associated with the early onset of plastic instability and with microstructural changes observed as function of the strain. Grain growth induced by deformation seems to be important during the first stage of deformation of this alloy. However, when ε > 0.4 this growth is accompanied by other microstructural rearrangements. These results suggest that in this alloy, a grain boundary sliding mechanism acts to allow a steady superplastic flow only for ε < 0.4. For ε values between 0.4 and 0.7, observed occurrences of microstructural changes and severe neck formation lead to the supposition that there is a transition in the deformation mechanism. These changes are more evident when ε > 0.7 as another mechanism is thought to take over.

36 MATERIALS SCIENCE↗

Material erosion measurements and expected operational lifetime of a deployable photon sieve payload

Spacecraft operating in low-Earth orbit are subjected to a number of hazardous environmental constituents that can lead to decreased system performance and reduced operational lifetimes. Due to their thermal, optical, and mechanical properties, polymers are used extensively in space systems; however they are particularly susceptible to material erosion and degradation as a result of exposure to the LEO environment. The focus of this research is to examine the material erosion and mass loss experienced by a custom Kaptonlike polyimide due to exposure in a simulated low-earth orbit environment. The deployable membrane telescope design discussed in this research is named Peregrine and is the scientific payload for FalconSat-7, a 3U cubesat designed and developed at the United States Air Force Academy (USAFA) for the purpose of demonstrating the capability of deployable membrane telescope technology on a nanosatellite platform. In addition to the polymer samples, chrome, silver and gold specimens will be examined to measure the oxidation rate and act as a control specimen, respectively. A magnetically filtered atomic oxygen plasma source has previously been developed and characterized for the purpose of simulating the low-Earth orbit environment. The plasma source can be operated at a variety of discharge currents and gas flow rates, of which the plasma parameters downstream of the source are dependent. The characteristics of the generated plasma were examined as a function of these operating parameters to optimize the production of O + ions with energy relevant to LEO applications. The erosion yield of the Kapton-like polyimide was experimentally determined to be 2.84 x 10 -24 cm 3 per atom which is in close agreement when compared to the on-orbit measurement for reaction efficiency of Kapton HN. We report the experimentally determined reaction rate for the Kapton-like polyimide was used to estimate the operational lifetime of the photon sieve during the solar conditions expected beginning in May 2019. The effective lifetime is estimated between 126 and 153 days.

36 MATERIALS SCIENCE↗

Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO 2 sequestration related conditions

The kinetic dissolution of Flagstaff Hill chlorite (CCa-2 from Clay Minerals Society), (Mg 4.55 Al 1.23 Fe 0.12 )(Al 1.04 Si 2.96 )O 10 (OH) 8 , was investigated using a well-mixed flow-through reactor at 100 °C, pH values ranging from 3.0 to 7.5, and variable saturation states. The objective was to measure the dependence of chlorite dissolution rate on pH as well as on degree of undersaturation under conditions applicable to geologic carbon storage. A batch experiment was conducted to determine the equilibrium constant of the dissolution reaction at 100 °C for the chlorite mineral phase used in this study. A series of experiments was run at varying CO 2 partial pressures (0–60 bars) and different flow rates (0.01–0.25 ml/min). Here, we use our experimental results in conjunction with previously published data to separate the effects of pH and solution saturation state. At constant pH, the chlorite dissolution rate decreases slowly as a function of the Gibbs free energy of reaction (ΔG r ), which is a quantitative measure of the degree of undersaturation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Grafted polythiophene pendent polymer brushes and their electronanopatterning

Here electrochemical nanolithography using grafted polymer brushes with terthiophene (3T) pendent was investigated. The film was fabricated by surface electropolymerization of a reversible addition-fragmentation chain-transfer agent macroinitiator containing a 3T pendant molecule and the subsequent polymer brush growth from a 3T functionalized methacrylate monomer (3T-Methacrylate). Electrochemical nanolithography and patterning were done using conducting atomic force microscopy (C-AFM) enabling precise nanopattern fabrication. In contrast to direct nanowriting, dip pen nanolithography, and nanolithographic additive manufacturing, the electrochemical nanolithography can be readily facilitated by applying a bias voltage between a conductive AFM tip and the grafted polymer brush film at ambient conditions and without ink transfer. The height and electrical resistance of the nanopatterns were dependent on the writing parameters (i.e. applied bias voltage and scan rate).

36 MATERIALS SCIENCE↗

Highly active Au/δ-MoC and Cu/δ-MoC catalysts for the conversion of CO 2 : The metal/C ratio as a key factor defining activity, selectivity, and stability

The ever growing increase of CO 2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO 2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO 2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo 2 C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO 2 conversion. Here, a control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrate Evolution in Response to Ongoing Environmental Shifts

Natural gas hydrates have the potential to become a vital domestic clean-burning energy source. However, past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. This project was designed to fill critical gaps in our understanding of domestic hydrate resources and improve forecasts for their response to environmental shifts. Project work can be separated into three interrelated components, each involving the development of predictive mathematical models. The first project component concerns the role of sediment properties on the development and dissociation of concentrated hydrate anomalies. To this end, we developed numerical models to predict equilibrium solubility of methane in twophase equilibrium with hydrate as a function of measureable porous medium characteristics. The second project component concerned the evolution of hydrate distribution in heterogeneous reservoirs. To this end, we developed numerical models to predict the growth and decay of anomalies in representative physical environments. The third project component concerned the stability of hydrate-bearing slopes under changing environmental conditions. To this end, we developed numerical treatments of pore pressure evolution and consolidation, then used "infinite-slope" analysis to approximate the landslide potential in representative physical environments, and developed a "rate-and-state" frictional formulation to assess the stability of finite slip patches that are hypothesized to develop in response to the dissociation of hydrate anomalies. The increased predictive capabilities that result from this work provide a framework for interpreting field observations of hydrate anomalies in terms of the history of environmental forcing that led to their development. Moreover, by taking explicit account of anomaly dissociation, project results are designed to help improve forecasts for changes in slope stability that could pose significant threats to energy infrastructure, disrupt hydrate reserves, and pollute the atmosphere with vast quantities of methane. This report presents the details of our work and outlines some of the highlights from our findings.

03 NATURAL GAS↗

A critical evaluation of two-equation models for near wall turbulence

A basic theoretical and computational study of two-equation models for near-wall turbulent flows was conducted. Two major problems established for the K-epsilon model are discussed, the lack of natural boundary conditions for the dissipation rate and the appearance of higher-order correlations in the balance of terms for the dissipation rate at the wall. The K-omega equation is shown to have two problems also: an exact viscous term is missing, and the destruction of the dissipation term is not properly damped near the wall. A new K-tau model (where tau = 1/omega is the turbulent time scale) was developed by inclusion of the exact viscous term, and by introduction of new wall damping functions with improved asymptotic behavior. A preliminary test of the new model yields improved predictions for the flat-plate turbulent boundary layer.

Speziale, Charles G.↗

CHANGO: A Software Tool for Boost Stage Guidance of the Space Launch System Exploration Mission 1

The Day of Launch Initiation Load Update (DOLILU) System is the means by which the Space Launch System (SLS) Vehicle trajectory is designed, verified, and uploaded on the Day of Launch (DOL) in order to ensure a safe flight. Launch vehicles are designed to fly down a narrow angle of attack and sideslip angle corridor in order to keep them within structural load limits. The angle of attack and sideslip angle response to the launch vehicle experiences can vary significantly based upon the winds experienced on the DOL. SLS Boost Stage flight employs an open-loop guidance scheme through Solid Rocket Booster (SRB) separation. In the SLS open-loop scheme, the vehicle will fly a prescribed set of attitudes as a function of the change in altitude since launch. This set of reference attitude values and corresponding altitude reference independent values are designed with ground software using winds measured on the DOL with the goal of minimizing angle of attack and sideslip angle, thereby minimizing related ascent integrated vehicle structural loads. The table of Boost Stage attitude commands as a function of altitude gained since launch is called the chi table. A software tool called CHANGO (Chi Angle Optimizer) designs the Boost Stage chi table which is uploaded to the vehicle’s flight computer and used during ascent by the flight software (FSW). The wind and atmospheric conditions are measured prior to launch and pre-processed to become input to the CHANGO software along with a set of parameters developed in advance of the DOL. CHANGO’s target set consists of the heading and altitude rate at SRB separation determined well before launch by the Program to Optimize Simulated Trajectories (POST). CHANGO consists of a simplified three degree-of-freedom (3-DOF) simulation representing the SLS launch configuration. In general, the launch azimuth is strongly correlated with the heading at SRB separation, and the initial pitchover rate is strongly correlated with the altitude rate at SRB separation. CHANGO uses an adaptation of Powell’s method to vary the initial pitchover rate and launch azimuth to solve a 2-dimentional minimization problem. CHANGO’s trajectory simulation is phase-based, with flight events separating the phases. Each flight phase has different attitude alignment logic. CHANGO’s 3-DOF simulation starts when the vehicle’s thrust-to-weight ratio equals one, and ends at a pre-calculated SRB separation time.

Ahmad, Naeem↗

Laser-Induced Fluorescence Measurements of Energetic Ions in a 100-A LaB6 Hollow Cathode

Increasingly long-duration space missions require a better understanding of the failure mechanisms of hollow cathodes to enable prediction of lifetime. Energetic ions have been measured in the plume of hollow cathodes but the energies are higher than can be explained classically. One of the mechanisms that appears to be contributing to the ion heating is ion acoustic turbulence (IAT), which has been investigated with plasma probes recently at JPL. In this work the ion velocity distribution has been measured using laser-induced fluorescence (LIF) at several high-current operating conditions on the centerline of a 100 A class hollow cathode at JPL. A retarding potential analyzer was (RPA) was used to measure the ion energy profile in the far plume and a Langmuir probe was used to measure electron temperature and plasma potential fluctuations. RPA energies are shown to correlate with the values measured by LIF. The ion temperature is shown to increase with distance downstream of the cathode. A parametric study of the ion heating as a function of discharge current and cathode flow rate was performed. It was found that for increasing current the ion temperature evolution did not vary even though the wave IAT wave energy increased. The effect of flow rate was more pronounced, with higher values reducing both ion temperature and wave energy linearly. These results indicate that IAT is at least partially responsible for energetic ion production in the hollow cathode plume.

Dodson, Christopher A.↗

Coupled Reactor Multiphysics and Mass Scalability Assessment for Crewed Megawatt-Class NEP System Architectures

Nuclear Electric Propulsion (NEP) is an in-space propulsion technology capable of enabling opposition and conjunction class crewed Mars missions. NEP subsystems include the reactor for heat generation, a power conversion system (PCS), power management and distribution (PMAD), electric propulsion subsystem (EPS), and a primary heat rejection system. Specific mass, or αe (kg / kWe), is a key performance parameter (KPP) of the propulsion system which is directly scalable with the performance and mass estimates for individual components. To inform technology maturation planning, full system and component level parametric modeling is ongoing to explore the design trade space and illustrate the effect of subsystem design choices on the system KPPs. In this study, scaling of high-assay, low-enriched uranium (HALEU) reactor designs is assessed through coupled reactor physics and thermal hydraulics analyses. Scaling analyses evaluate the impact of system performance parameters (power level, interface temperatures) on mass for direct gas cooled, pumped liquid metal, and passively cooled heat pipe reactor concepts. Each concept requires specific geometries and working fluids to reach the performance goals of PCS interface conditions (temperature, pressure, flow rate) and system mass. The reactor assembly includes the active core (fuel, moderator, cladding, working fluid), axial and radial neutron reflectors, control drums, structural support / pressure vessel, and external radiation shielding. Each of these components are parametrically sized based on performance parameters for a megawatt-class power cycle. Results of this scaling analysis increase NEP propulsion system modeling fidelity and ultimately aim to support technology down-selection along with related technology development planning. The reactor and shield αe are a function of several PCS design choices, and reactor scaling with these parameters must be considered to enable an informed decision on reactor geometry and working fluid combination.

Nuclear Electric Propulsion↗

Characterization of Residual Stress as a Function of Friction Stir Welding Parameters in Oxide Dispersion Strengthened (ODS) Steel MA956

This article characterizes the residual stresses generated by friction stir welding of oxide dispersion strengthened steel MA956 over a series of welding conditions. A plate of MA956 steel was friction stir welded at three conditions: 500 rpm/25 millimeters per minute (mmpm), 400 rpm/50 mmpm and 400 rpm/100 mmpm. The residual stresses across these welds were measured using both x-ray and neutron diffraction techniques. Longitudinal residual stresses up to eighty percent of the yield strength were observed for the 400 rpm/100 mmpm condition. Increasing the traverse rate while holding the rotational speed fixed increased the residual stress levels in the stir zone and at the stir zone-thermomechanically affected zone interface. The stress profiles displayed the characteristic M shape, and the asymmetry between advancing and retreating stress peaks was limited, occurring mainly on the root side of the weld. The large magnitude of the stresses was maintained throughout the thickness of the plates.

36 MATERIALS SCIENCE↗

Review of spaceflight and hindlimb suspension unloading induced sarcomere damage and repair

Hindlimb suspension unloading (HSU) and spaceflight microgravity induce atrophy of the slow adductor longus muscle fibers which, following reloading, exhibit eccentric contraction (EC)-like lesions (abnormal widening of sarcomeres with A band disruption and excessively wavy, extracted Z lines). These lesions are similar morphologically to those produced in normal muscles after strenuous eccentric exercise. It appears that atrophic muscles exhibit increased susceptibility to eccentric damage because lesions are produced during nonstressful voluntary movements upon return to weightbearing. The EC-like lesions are absent in the unweighted conditions, but appear in HSU rats 15-60 minutes after reloading and in space-flown rates about 4 hrs after landing. By 12 hours, many EC-like lesioned sarcomeres are fully covered by longitudinal patches of Z line-like material which increases in density by 48 hours, producing the so-called "Z line streaming" morphology. In this case, Z line streaming is indicative of rapid repair of damaged sarcomeres rather than the onset of sarcomere breakdown. Immunoelectron microscopy is necessary to determine the composition of this dense material. By 9 days of reloading at 1 gravity, sarcomeres have regained normal structure, except for very rare persistence of faint Z patches. The morphological data indicate that Z patches serve at least two functions: 1) to permit contractile force to be transmitted across the damaged sarcomeres and 2) to provide a scaffold upon which sarcomeres are reconstructed in an active functional muscle.

NASA Discipline Number 00-00↗

PV backsheets survey protocol: A framework for geo-spatial field surveys for bulk material characterization and reliability analysis applied across 41 PV systems

As widespread adoption of photovoltaic (PV) technologies continues, understanding the lifetime of modules is paramount to the viability of the industry as an environmentally conscious alternative to traditional energy generation. Although power degradation can affect the total energy production of a module over its lifetime, module safety failures necessitate the removal of a module leading to a loss of not only the particular asset, but the earning potential of the device. Therefore, it is critical to ensure that the components that provide essential safety functions for PV module operate for their entire rated lifetime. PV backsheets provide necessary electrical insulation to the completed device and failure of this component is cause for a immediate removal of the module. Degradation of the PV module backsheet has led to module safety failures in large-scale installations, costing millions of dollars in damages and lost potential revenue. The spatio-temporal degradation of fielded PV modules is important to study in order to identify which modules within installations are experiencing the greatest exposure conditions and in turn have the highest chance of failure. This paper describes a comprehensive field survey protocol developed for monitoring PV module backsheet performance using solely non-destructive methods in commercial PV fields. The protocol establishes a field naming convention, sampling method, data handling requirements, and measurement procedures. By ensuring consistent data collection practices, the field survey protocol enables research groups to obtain data of uniform quality on backsheet performance over multiple years and locations. In this study, the developed protocol was implemented at forty-one PV sites. Eight different types of airside layer backsheet materials including poly(vinylidene fluoride) (PVDF), acrylic PVDF, poly(tetrafluoroethylene-co-hexafluoropropylene-co-vinylidene fluoride) (THV), poly(vinyl fluoride) (PVF), poly(ethylene terephthalate) (PET), fluoroethylene vinyl ether (FEVE), polyethylene naphthalate (PEN), and glass were identified using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The field survey results show that the spatial distribution of degradation indicators are non-uniform within a particular module, individual site, and across site locations. The degradation of PV modules increased in severity for modules mounted at the edge of rows (across a field) and near the junction box (within a module). This study demonstrates the sensitivity of material performance to exposure length across different materials and climates.

14 SOLAR ENERGY↗

Synthesis and Characterization of [Ni(H 2 O)(7-P Ph 2 N ArSO3 ) 2 ](NaBF 4 ) for Light-Driven Quantum Dot-Catalyst Hydrogen Evolution

Light-driven hydrogen generation from water is a route to carbon-neutral fuels. However, the integrated light absorbers and catalysts must be compatible and functional under the same conditions. A sulfate-functionalized complex, [Ni(H 2 O)(7-P Ph 2 N ArSO3 ) 2 ](NaBF 4 ), where P Ph 2 N ArSO3 = 4-(3,6-diphenyl-1,3,6-azadiphosphepan-1-yl)benzenesulfonate), was synthesized and characterized. A solid-state structure from single-crystal X-ray crystallography is also reported. The electrocatalytic activity for hydrogen evolution of this complex in 7:3 H 2 O:CH 3 CN was characterized by cyclic voltammetry and controlled potential electrolysis, with a maximum observed rate of 83 s –1 . Density functional theory was used to characterize the favorable binding of the sulfate functionalities to cadmium sulfide quantum dots. Experimental assembly of these catalysts onto cadmium sulfide quantum dots was successful. In conclusion, both fast electron transfer and light-driven pH-dependent hydrogen evolution were observed.

36 MATERIALS SCIENCE↗