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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 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Nanosecond, Time-Resolved Shift of the Photoluminescence Spectra of Organic, Lead-Halide Perovskites Reveals Structural Features Resulting from Excess Organic Ammonium Halide

The effort to drive solution-based perovskite solar cells toward higher efficiency has been considerable, reaching over 24%. Such progress has been made possible by the low-energy barrier to crystallization. The low-energy barrier in the reverse direction, however, also renders them susceptible to dissociation from heat, moisture, and photoexcitation. Consequently, studies that provide information on the stability of perovskites are of considerable importance. It has been reported that perovskite crystals formed using different stoichiometries of the organic precursors and metal halide are equivalent. Our findings, however, suggest that the difference in reaction pathways affects the quality of the final crystal and that changes in morphology and the production of any defects can lead to differences in behavior under illumination. Here, we present photoluminescence spectra subsequent to nanosecond photoexcitation of perovskites synthesized under various conditions. Our results indicate that the presence of excess precursors (i.e., CH 3 NH 3 X, X = I and surfactant) gives rise to an ~20 ns relaxation time with which the photoluminescence spectrum achieves its equilibrium value. This relaxation is absent in bulk, polycrystalline materials. This is, to our knowledge, the first report of the ~20 ns relaxation time, which we attribute to cation migration. Furthermore, these structural changes are not detectable subsequent to photoexcitation by X-ray diffraction nor are they detectable by in situ X-ray diffraction during photoexcitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis

Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar “bda” ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore. Nevertheless, synthesis of heterogeneous Ru(II)(bda) complexes remains challenging. We discuss here a new “bottom-up” synthetic method for immobilizing these catalysts at the surface of a photoanode for use in a dye-sensitized photoelectrosynthesis cell (DSPEC). The procedure provides a basis for rapidly screening the role of ligand variations at the catalyst in order to understand the impact on device performance. The best results of a water-oxidation DSPEC photoanode based on this procedure reached 1.4 mA/cm 2 at pH 7 in 0.1 M [PO 4 H 2 ]-/[PO 4 H] 2- solution with minimal loss in catalytic behavior over 30 min, and produced an incident photon to current efficiency (IPCE) of 24.8% at 440 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Superlattice by charged block copolymer self-assembly

Charged block copolymers are of great interest due to their unique self-assembly and physicochemical properties. Understanding of the phase behavior of charged block copolymers, however, is still at a primitive stage. Here we report the discovery of an intriguing superlattice morphology from compositionally symmetric charged block copolymers, poly[(oligo(ethylene glycol) methyl ether methacrylate–co–oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]–b–polystyrene (POEGMA–PS), achieved by systematic variation of the molecular structure in general, and the charge content in particular. POEGMA–PS self-assembles into a superlattice lamellar morphology, a previously unknown class of diblock nanostructures, but strikingly similar to oxygen-deficient perovskite derivatives, when the fraction of charged groups in the POEGMA block is about 5–25%. The charge fraction and the tethering of the ionic groups both play critical roles in driving the superlattice formation. This study highlights the accessibility of superlattice morphologies by introducing charges in a controlled manner.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Flux line relaxation kinetics following current quenches in disordered type-II superconductors

We investigate the relaxation dynamics of magnetic vortex lines in type-II superconductors following rapid changes of the external driving current by means of an elastic line model simulated with Langevin molecular dynamics. A system of flux vortices in a sample with randomly distributed point-like defects is subjected to an external current of appropriate strength for a sufficient period of time so as to be in a moving non-equilibrium steady state. Here, the current is then instantaneously lowered to a value that pertains to either the moving or pinned regime. The ensuing relaxation of the flux lines is studied via one-time observables such as their mean velocity and radius of gyration. We have in addition measured the two-time flux line height autocorrelation function to investigate dynamical scaling and aging behavior in the system, which in particular emerge after quenches into the glassy pinned state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1993

An X-ray excited wind in Centaurus X-3

We propose a new interpretation of the behavior of the notable X-ray binary source Centaurus X-3. Based on both theoretical and observational arguments (using EXOSAT data), we suggest that an X-ray excited wind emanating from the O star is present in this system. Further, we suggest that this wind is responsible for the mass transfer in the system rather than Roche-lobe overflow or a normal radiatively driven stellar wind. We show that the ionization conditions in Cen X-3 are too extreme to permit a normal radiatively driven wind to emanate from portions of the stellar surface facing toward the neutron star. In addition, the flux of X-rays from the neutron star is strong enough to drive a thermal wind from the O star with sufficient mass-flux to power the X-ray source. We find that this model can reasonably account for the long duration of the eclipse transitions and other observed features of Cen X-3. If confirmed, this will be the first example of an X-ray excited wind in a massive binary. We also discuss the relationship between the excited wind in Cen X-3 to the situation in eclipsing millisecond pulsars, where an excited wind is also believed to be present.

Day, C. S. R.↗
NASA NTRS2015

Space Synthetic Biology Project

Synthetic biology is an effort to make genetic engineering more useful by standardizing sections of genetic code. By standardizing genetic components, biological engineering will become much more similar to traditional fields of engineering, in which well-defined components and subsystems are readily available in markets. Specifications of the behavior of those components and subsystems can be used to model a system which incorporates them. Then, the behavior of the novel system can be simulated and optimized. Finally, the components and subsystems can be purchased and assembled to create the optimized system, which most often will exhibit behavior similar to that indicated by the model. The Space Synthetic Biology project began in 2012 as a multi-Center effort. The purpose of this project was to harness Synthetic Biology principals to enable NASA's missions. A central target for application was to Environmental Control & Life Support (ECLS). Engineers from NASA Marshall Space Flight Center's (MSFC's) ECLS Systems Development Branch (ES62) were brought into the project to contribute expertise in operational ECLS systems. Project lead scientists chose to pursue the development of bioelectrochemical technologies to spacecraft life support. Therefore, the ECLS element of the project became essentially an effort to develop a bioelectrochemical ECLS subsystem. Bioelectrochemical systems exploit the ability of many microorganisms to drive their metabolisms by direct or indirect utilization of electrical potential gradients. Whereas many microorganisms are capable of deriving the energy required for the processes of interest (such as carbon dioxide (CO2) fixation) from sunlight, it is believed that subsystems utilizing electrotrophs will exhibit smaller mass, volume, and power requirements than those that derive their energy from sunlight. In the first 2 years of the project, MSFC personnel conducted modeling, simulation, and conceptual design efforts to assist the project in selecting the best approaches to the application of bioelectrochemical technologies to ECLS. Figure 1 shows results of simulation of charge transport in an experimental system. Figure 2 shows one of five conceptual designs for ECLS subsystems based on bioelectrochemical reactors. Also during the first 2 years, some work was undertaken to gather fundamental data (conductivities, overpotentials) relevant to the modeling efforts.

Howard, David↗
DOE OSTI2019

Investigation of Powder Processing, Heat Treating, and Texturing to Improve Gas Atomized alnico Magnets for use in Electric Drive Motors

Alnico permanent magnet materials have been proposed as a rare earth free permanent magnet alternative during an ongoing search to replace rare earth permanent magnets that are used for interior permanent magnet motors, a common motor found in electric vehicles. A powder processing approach was used to study two alnico alloys (Full-Co and lower cost Co-Lean, both with enhanced coercivity) to anticipate high volume manufacturing needed to supply millions of permanent magnets to interior permanent magnet motors. In this study the two alloys were gas atomized, compression molded, and solid-state sintered to fabricate near-final shape alnico magnets. The Full-Co displayed abnormal grain growth (resulting in >1 mm size grains) during sintering while the Co-Lean did not (~20 μm – 400 μm sized grains depending on the sintering hold times). Solid state grain alignment was used to promote a <001> textured (easy axis) microstructure to enhance magnetic properties, yet both alloys did not show predicted grain alignment behavior. Comparisons of the powder processing, microstructures, and magnetic properties of the two alloys will be discussed, as well as an evaluation as to why non-theoretical processing behavior of the Full-Co and Co-Lean alnico permanent magnets is occurring. Preliminary interior permanent magnet motor designs for alnico magnets are discussed, as this is the overarching objective for powder-based alnico permanent magnets.

Rinko, Emily↗
DOE OSTI2026

Balancing moisture and oxygen can match the crystallization dynamics of inert halide perovskite processing

Understanding crystallization in ambient environments is essential for scaling the fabrication of halide perovskite solar cells. Antisolvent-free perovskite deposition offers improved compatibility with high-throughput processing but introduces distinct crystallization dynamics relative to the more ubiquitous use of antisolvents in lab-scale perovskite fabrication. These dynamics are driven by interactions between solutes, solvent and the deposition environment. Using in situ wide-angle X-ray scattering during spin-coating and annealing, we demonstrate how relative humidity (RH) and oxygen, can be tuned to drive polytype evolution during ambient crystallization of formamidinium lead iodide to match that of inert synthesis and achieve comparable film and device quality. In an inert (N 2 ) environment, we find that perovskite films follow a well-established 2H → 3C phase transformation with a short period of coexistence of the 4H and 6H phase during heating. During crystallization in dry air (RH 0%), the added presence of oxygen leads to the dominance of 4H intermediate for an extended duration, establishing a 2H → 4H → 3C pathway. Introducing low humidity (RH 10%) suppresses the 4H phase to a short-lived intermediate above 100 °C, facilitating a more direct transition to the desired 3C phase and almost replicating the crystallization behavior observed under inert conditions. Interestingly, films crystallized under RH 10% show a lower onset temperature for the perovskite 3C phase than under N 2 . At higher humidity (RH 40%), the strong interaction of oxygen and moisture with iodoplumbates appears to stabilize higher order polytypes (4H and 6H). Devices fabricated under RH 10% achieve higher efficiency and enhanced stability compared to those produced under inert atmosphere. These findings provide mechanistic insight into crystallization pathways in different environments and provide a framework to transfer processes from inert to ambient conditions. The results highlight the critical role of controlled humidity in tuning antisolvent-free perovskite crystallization for scalable processing.

Hossain, Maimur [Univ. of California, San Diego, C↗
NASA NTRS1996

Ionospheric convection during different phases of magnetospheric substorms

Observations of ionospheric convection flows at a range of local times during the various phases of the substorm cycle are reported on with the aim of investigating the convection behavior during a range of times and phases. The ionospheric flow observations are from the EISCAT and DMSP satellites. The substorm phases are identified from energetic particle measurements from geosynchronous satellites. The growth phase convection indicates an initial expansion of the polar cap. There is an unexplained poleward motion of the flow reversal boundary (FRB). It is concluded that this motion does not necessarily provide a true representation of the balance between reconnection at the dayside and in the tail. The expansion phase flows do not show any evidence for tail reconnection until late in the phase. The convection during the recovery phase is indicative of tail reconnection as there is evidence that there is only a lobe cell driving convection on the dayside.

Lester, M.↗
NASA NTRS2016

Using CubeSats to Monitor Debris Flux

Recent updates to NASA's Orbital Debris Engineering Model (ORDEM 3.0) include a population of small particles (1-2 mm in size) composed of high-density materials (e.g., steel) that drive much of the predicted risk for satellites in the 700-1000 km altitude regime. This modeled population was based on the analysis of returned surfaces of the Shuttle, which flew below 600 km altitude. The cessation of Shuttle missions, plus the lack of in situ data above 600 km means that a data source is being sought to either confirm or modify this high-density population. One possible data source would be a database of anomalous sporadic changes in spacecraft orbit/orientation that might be due to momentum transfer from small particles too small to seriously damage the spacecraft. Because the momentum imparted from an impact would be tiny, it would most likely show up in the orbital behavior of cubesats and other small satellites. While such small satellites were few in number, this was not a particularly attractive option, but now with the proliferation of cubesats in multiple orbit planes and altitudes, the possible collecting area has increased significantly. This presentation will discuss the physics of momentum-transferring impacts from hypervelocity collisions, and make predictions about rates, directions, and locations of such impacts. In addition, it will include recommendations for satellite users on what kind of data might be worth archiving and investigating.

Matney, Mark↗
NASA NTRS2024

Molecular Dynamics Simulations of Microstructural Effects on Austenite-Martensite Interfaces in NiTi

Formation and migration of austenite-martensite interfaces plays the key role in reversible martensitic transformations of shape memory alloys (SMAs). How these interfaces interact with the SMA microstructure is a primary determining factor in important functional properties such as hysteresis and transformation span. As such, successful microstructural engineering of SMAs requires in-depth knowledge of interface behavior. The rapid nature of martensitic transformations makes experimental observations of moving austenite-martensite interfaces challenging. Molecular dynamics (MD) simulation is a unique tool which can probe the atomic-scale details of austenite-martensite interfaces as they migrate through different microstructures. However, in focusing on the entire transformation process, including the nucleation of new phases, MD studies are usually performed so far from equilibrium that their relevance to experiment is questionable. Here, we demonstrate new MD techniques to generate energetically preferred austenite-martensite interfaces in NiTi under near-equilibrium conditions. The interfaces are semi-coherent, exhibiting a series of structural disconnections, and they can migrate rapidly through single crystals under only small thermodynamic driving forces. In contrast, when interfaces migrate in polycrystals, their motion is impeded by thermoelastic effects as well as changes in orientation relationships at grain boundaries. Microstructures which accumulate large amounts of elastic energy tend to release some fraction through irreversible, hysteresis-inducing mechanisms. We demonstrate that engineering microstructures with less constraints is a viable strategy to produce SMAs with reduced hysteresis and transformation span. Similar thermoelastic and hysteresis-inducing mechanisms also arise when austenite-martensite interfaces encounter precipitates and can be controlled by tuning characteristics of the precipitate distribution.

Gabriel Plummer↗
NASA NTRSDate not supplied

Molecular Dynamics Simulations of Microstructural Effects on Austenite-Martensite Interfaces in NiTi

The formation and migration of austenite-martensite interfaces plays the key role in reversible martensitic transformations of shape memory alloys (SMAs). How these interfaces interact with the SMA microstructure is a primary determining factor in important functional properties such as hysteresis and transformation span. As such, successful microstructural engineering of SMAs requires in-depth knowledge of interface behavior. The rapid nature of martensitic transformations makes experimental observations of moving austenite-martensite interfaces challenging. Molecular dynamics (MD) simulation is a unique tool which can probe the atomic-scale details of austenite-martensite interfaces as they migrate through different microstructures. However, in focusing on the entire transformation process, including the nucleation of new phases, MD studies are usually performed so far from equilibrium that their relevance to experiment is questionable. Here, we demonstrate new MD techniques to generate energetically preferred austenite-martensite interfaces in NiTi under near-equilibrium conditions. The interfaces are semi-coherent, exhibiting a series of structural disconnections, and they can migrate rapidly through single crystals under only small thermodynamic driving forces. In contrast, when interfaces migrate in polycrystals, their motion is impeded by thermoelastic effects as well as changes in orientation relationships at grain boundaries. Microstructures which accumulate large amounts of elastic energy tend to release some fraction through irreversible, hysteresis-inducing mechanisms. We demonstrate that engineering microstructures with less constraints is a viable strategy to produce SMAs with reduced hysteresis and transformation span. Similar thermoelastic and hysteresis-inducing mechanisms also arise when austenite-martensite interfaces encounter precipitates and can be controlled by tuning characteristics of the precipitate distribution.

Gabriel Plummer↗
NASA NTRSDate not supplied

Molecular Dynamics Simulations of Microstructural Effects on Austenite-Martensite Interfaces in NiTi

Formation and migration of austenite-martensite interfaces plays the key role in reversible martensitic transformations of shape memory alloys (SMAs). How these interfaces interact with the SMA microstructure is a primary determining factor in important functional properties such as hysteresis and transformation span. As such, successful microstructural engineering of SMAs requires in-depth knowledge of interface behavior. The rapid nature of martensitic transformations makes experimental observations of moving austenite-martensite interfaces challenging. Molecular dynamics (MD) simulation is a unique tool which can probe the atomic-scale details of austenite-martensite interfaces as they migrate through different microstructures. However, in focusing on the entire transformation process, including the nucleation of new phases, MD studies are usually performed so far from equilibrium that their relevance to experiment is questionable. Here, we demonstrate new MD techniques to generate energetically preferred austenite-martensite interfaces in NiTi under near-equilibrium conditions. The interfaces are semi-coherent, exhibiting a series of structural disconnections, and they can migrate rapidly through single crystals under only small thermodynamic driving forces. In contrast, when interfaces migrate in polycrystals, their motion is impeded by thermoelastic effects as well as changes in orientation relationships at grain boundaries. Microstructures which accumulate large amounts of elastic energy tend to release some fraction through irreversible, hysteresis-inducing mechanisms. We demonstrate that engineering microstructures with less constraints is a viable strategy to produce SMAs with reduced hysteresis and transformation span. Similar thermoelastic and hysteresis-inducing mechanisms also arise when austenite-martensite interfaces encounter precipitates and can be controlled by tuning characteristics of the precipitate distribution.

Gabriel Plummer↗
DOE OSTI2025

Pressure‐Induced Structural and Optoelectronic Modulations in 2D Dion‐Jacobson Hybrid Lead Iodide Perovskites With a Rigid Spacer

2D hybrid organic-inorganic perovskites (HOIPs) are known for their superior chemical and thermal stability over 3D variants, positioning them as promising materials for advanced optoelectronic applications. Applying external high pressure is an effective strategy to modify their structures and tune their optoelectronic properties. This study examines the high-pressure behavior of a Dion-Jacobson type 2D HOIP, DPDAPbI 4 , which incorporates the rigid organic spacer N,N-dimethylphenylene-p-diammonium (DPDA). Utilizing photoluminescence, UV–visible absorption, vibrational spectroscopy, and in situ synchrotron powder X-ray diffraction, an isostructural phase transition is identified near 1.5 GPa, marked by a notable shift in photoluminescence intensity linked to free exciton emission. Synchrotron X-ray diffraction reveals significant anisotropic compression along the c-axis, while structural analysis indicates the rare phenomenon of reduced lead-iodide octahedral distortion below 2 GPa, contrasting with the increased octahedral distortion reported in most previous studies on lead-based 2D HOIPs. Density functional theory calculations elucidate the structural origins and mechanisms driving the pressure-induced phase transition and optoelectronic tuning. These findings underscore the critical interplay between rigid organic spacers and inorganic octahedra in modulating high-pressure optoelectronic properties, offering valuable insights for designing future 2D HOIPs with tailored functionalities.

14 SOLAR ENERGY↗
DOE OSTI2020

Spectroscopic characterization of a new Re(i) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications

This work describes the preparation of a new thiosemicarbazone derivative, (Z)- N -ethyl-2-(6-oxo-1,10-phenanthrolin-5(6 H )-ylidene)hydrazinecarbothioamide (phet) and its respective Re( I ) tricarbonyl chloro complex, fac -[ReCl(CO) 3 (phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac -[ReCl(CO) 3 (phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCT Re→phet and IL phet(n→π*) transitions. The absorption bands and emission quantum yields of fac -[ReCl(CO) 3 (phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn 2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc + /Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the Re I/0 reduction and consequent Cl - release. Furthermore, the new complex was able to act as an electrocatalyst for CO 2 reduction into CO ( E onset = -1.92 V vs. Fc + /Fc), with a turnover frequency of 2.81 s -1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re( I ) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re( I )-thiosemicarbazone derivatives for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

Sinusoidal input describing function for hysteresis followed by elementary backlash

The author proposes a new sinusoidal input describing function which accounts for the serial combination of hysteresis followed by elementary backlash in a single nonlinear element. The output of the hysteresis element drives the elementary backlash element. Various analytical forms of the describing function are given, depending on the a/A ratio, where a is the half width of the hysteresis band or backlash gap, and A is the amplitude of the assumed input sinusoid, and on the value of the parameter representing the fraction of a attributed to the backlash characteristic. The negative inverse describing function is plotted on a gain-phase plot, and it is seen that a relatively small amount of backlash leads to domination of the backlash character in the describing function. The extent of the region of the gain-phase plane covered by the describing function is such as to guarantee some form of limit cycle behavior in most closed-loop systems.

Ringland, R. F.↗
DOE OSTI2021

A systematic solution to quantify economic values of vehicle grid integration

We report Vehicle-Grid-Integration (VGI) supplies one of the potential benefit extensions for electric vehicles (EVs) to make use of their parking time, which enables the EVs to provide grid services while still meeting consumer driving needs. However, the costs, benefits and risks of VGI still remain unclear, which limits the development of the VGI to promote the interaction between the EV and grid. In this study, we propose an integrated framework to quantify and utilize the aggregate flexibility of the EVs to supply the grid services in electricity markets. The integrated solution includes five sub-modules that cover end-to-end functionalities from individual EV energy consumption estimation to final monetary values calculation of providing grid services. Both wholesale market and local level charging management are formulated in the optimization module. A predictive control algorithm is proposed to allocate power to individual vehicles in real time, considering uncertainties from dispatch signal and travel behavior. Simulation results from 10,000 EVs indicate that the proposed optimization methods can significantly reduce the system cost in both wholesale market and retail market. Local tariff optimization reduces the electricity cost by 24.4% compared to uncontrolled charging. Wholesale market optimization results show that $\$$691 and $\$$255 revenues can be captured by each EV in ERCOT and CAISO markets per year, although with a conservative assumption on battery throughput cost at 0.16$\$$/kWh.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer

Two-electron, one-proton reactions of a family of [CoCp(dxpe)(NCCH 3 )] 2+ complexes (Cp = cyclopentadienyl, dxpe = 1,2-bis(di(aryl/alkyl)phosphino)ethane) form the corresponding hydride species [HCoCp(dxpe)] + through a stepwise proton-coupled electron transfer process. For three [CoCp(dxpe)(NCCH 3 )] 2+ complexes (dxpe = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), and dcpe (1,2-bis(dicyclohexylphosphino)ethane)), peak shift analysis was employed to quantify apparent proton transfer rate constants from cyclic voltammograms recorded with acids ranging 22 pK a units. The apparent proton transfer rate constants correlate with the strength of the proton source for weak acids, but these apparent proton transfer rate constants curiously plateau (k pl ) as the reaction becomes increasingly exergonic. The absolute apparent proton transfer rate constants across both these regions correlate with the steric bulk of the chelating diphosphine ligand, with bulkier ligands leading to slower kinetics (k plateau,depe = 3.5 x 10 7 M -1 s -1 , k plateau,dppe = 1.7 x 10 7 M -1 s -1 , k plateau,dcpe = 7.1 x 10 4 M -1 s -1 ). Mechanistic studies were conducted to identify the cause of the aberrant $k_PT^{app}$–ΔpK a trends. When the deuterated acids are employed, deuterium incorporation in the Cp ring is observed, indicating protonation of the CoCp(dxpe) species to form the corresponding hydride proceeds via initial ligand protonation. Digital simulations of cyclic voltammograms show ligand loss accompanying initial reduction gates subsequent PCET activity at higher driving forces. Together, these experiments reveal the details of the reaction mechanism: reduction of the Co(III) species is followed by dissociation of the bound acetonitrile ligand, subsequent reduction of the unligated Co(II) species to form a Co(I) species is followed by protonation, which occurs at the Cp ring, followed by tautomerization to generate the stable Co(III)-hydride product [HCoCp(dxpe)] + . Analysis as a function of chelating disphosphine ligand, solvent, and acid strength reveals that the ligand dissociation equilibrium is directly influenced by the steric bulk of the phosphine ligands and gates protonation, giving rise to the plateau of apparent proton transfer rate constant with strong acids. The complexity of the reaction mechanism underpinning hydride formation, encompassing dynamic behavior of the entire ligand set, highlights the critical need to understand elementary reaction steps in proton-coupled electron transfer reactions.

14 SOLAR ENERGY↗