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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 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Diamagnetic field states in cosmological plasmas

Using a generally covariant electrovortic (magnetofluid) formalism for relativistic plasmas, the dynamical evolution of a generalized vorticity (a combination of the magnetic and kinematic parts) is studied in a cosmological context. We derive macroscopic vorticity and magnetic field structures that can emerge in spatial equilibrium configurations of the relativistic plasma. Furthermore, these fields, however, evolve in time. These magnetic and velocity fields, self-consistently sustained in a plasma with arbitrary thermodynamics, constitute a diamagnetic state in the expanding universe. In particular, we explore a special class of magnetic and velocity field structures supported by a plasma in which the generalized vorticity vanishes. We derive a highly interesting characteristic of such “superconductor-like” fields in a cosmological plasmas in the radiation era in the early universe. In that case, the fields grow proportional to the scale factor, establishing a deep connection between the expanding universe and the primordial magnetic fields.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

The dark components of the Universe are slowly clarified

The dark sector of the Universe is beginning to be clarified step by step. If the dark energy is vacuum energy, then 123 orders of this energy are reduced by ordinary physical processes. For many years, these unexplained orders were called a crisis of physics. There was indeed a “crisis” before the introduction of the holographic principle and entropic force in physics. The vacuum energy was spent on the generation of new quantum states during the entire life of the Universe, but in the initial period of its evolution the vacuum energy (78 orders) were reduced more effectively by the vacuum condensates produced by phase transitions, because the Universe lost the high symmetry during its expansion. Important problems of physical cosmology can be solved if the quarks, leptons, and gauge bosons are composite particles. The dark matter, partially or all consisting of familon-type pseudo-Goldstone bosons with a mass of 10{sup —5}–10{sup –3} eV, can be explained in the composite model. Three generations of elementary particles are absolutely necessary in this model. In addition, this model realizes three relativistic phase transitions in a medium of familons at different redshifts, forming a large-scale structure of dark matter that was “repeated” by baryons. We predict the detection of dark energy dynamics, the detection of familons as dark matter particles, and the development of spectroscopy for the dark medium due to the probable presence of dark atoms in it. Other viewpoints on the dark components of the Universe are also discussed briefly.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Additive manufacturing of metal matrix composites

Although Metal matrix composites (MMCs) are superior to most sought-after metallic alloys, their challenging fabricability has limited their widespread use in bulk-form applications. Among the many advanced fabrication techniques, Additive Manufacturing (AM), owing to its unique capabilities to produce near-net shapes, has drawn significant traction in the past two decades, especially for materials that are difficult to process using traditional methods. However, unlike pure metal/alloy systems, MMCs are highly sensitive to the processing conditions prevailing in AM techniques due to factors such as the high melting point of reinforcement particles and the potential for in-situ reactions. Therefore, it may be a while before metal matrix composites are commercially produced via AM. This review will discuss the current state-of-the-art design, fabricability, and performance of various additively manufactured MMCs. A particular focus will be on microstructural evolution and microstructure-property relationships. The most employed AM techniques, such as directed energy deposition, powder bed fusion, binder jetting, sheet lamination, and solid-state friction stir processing, are fundamentally different in terms of thermo-kinetics, forming the perspective for this review. A detailed comparison of microstructural evolution and process parameter optimization, including feedstock preparation methods and the role of machine learning and modeling among the different AM processes, is also presented. Finally, a critical evaluation of emerging AM technologies for MMCs is also provided, highlighting their potential advantages and challenges.

36 - MATERIALS SCIENCE↗
DOE OSTI2026

Role of the Character of the Excited State of Singly Reduced Rh 2 (II,II) Intermediates on Photocatalytic Activity

Singly reduced intermediates have recently been implicated as photoactive intermediates in a number of important reactions; however, their photophysical properties remain poorly understood. A series of dirhodium(II,II) complexes, cis-[Rh 2 (p-R-Form) 2 (bncn) 2 ] 2+ (bncn = benzo[c]cinnoline; p-R-Form = N,N′-di-p-R-phenylformamidinate), where R = −OCH 3 (1), −CH 3 (2), −H (3), −F (4), −Cl (5), and −CF 3 (6), and their respective radical anions were prepared and their excited state properties were investigated. Complex 3 acted as a singlemolecule photocatalyst for H 2 production with red light. Substitution on the formamidinate ligands in 1−6 affected the energy of the Rh 2 (δ*)/Form(π,nb) highest occupied molecular orbital (HOMO), consistent with the metal/ligand-to-ligand charge transfer ( 1 ML-LCT) absorption maxima and the 3 ML-LCT excited state lifetime, ranging from 1.6 ns in 1 to 54 ns in 6 in CH 3 CN. The highest turnover number for photocatalytic H 2 evolution was observed for 3, and the lowest values were for 1 and 6. The radical anion, [Rh 2 ] − , formed during photocatalysis, was shown to absorb a photon and undergo a second reduction. The lifetimes of the doublet excited states of [3] − and [6] − were 0.49 and 0.24 ns, respectively. Calculations showed that the lowest energy excited state in [3] − was 2 ML-LCT, whereas that in [6] − was a bncn − → Rh 2 (σ*) ligand-to-metal charge transfer ( 2 LMCT) state. The 2 LMCT state stabilized across the series from [1] − to [6] − , pointing at its role in modulating the photophysical properties. This work highlights the importance of the reductive quenching of [Rh 2 ] − and the generation of the doubly reduced species to effectively catalyze hydrogen evolution.

Absorption↗
DOE OSTI2022

Thermo-Mechanical Distortion of Tungsten-Coated Steel During High Heat Flux Testing Using Plasma Arc Lamps

An experimental setup and a test section were designed and fabricated for high heat flux testing (HHFT) of neutron-irradiated specimens using water-wall plasma arc lamps. Because of the radiological considerations and limitations of reactor irradiation, the size of the test articles was limited to disks less than 10 mm in diameter. The specimen was clamped onto an actively cooled block, and clamping allowed the insertion of several thermocouples on the back surface of the specimen through a copper (Cu) block. Five vacuum plasma sprayed tungsten (W)–coated F82H steel specimens were subjected to HHFT. Surface profilometry measurements, which were conducted after HHFT, revealed central bowing of the top W surface. This type of residual distortion occurred for all of the specimens, and the larger the specimens were, the larger was the distortion.In an attempt to understand specimen distortion and address the science questions related to the testing of subsize specimens during HHFT, a simplified thermo-mechanical model was developed. By using a measured temperature in the Cu as an isothermal boundary condition, the model eliminated the need for coupling cooling fluid flow models with stress models, greatly simplifying the analysis. The main variable in the proposed model is hC, i.e., the thermal contact conductance between the F82H and the Cu washer. Inelastic properties, including hardening properties, were considered for F82H steel and Cu. Numerical simulation results demonstrated a buildup of residual deformation during HHFT and a very complex state of stress and deformation during typical heat flux (HF) cycling. Additionally, hoop stress evolution during a high heat flux cycle reveals that F82H at an interface with W would be mainly in compression during HF application and experienced a transition to a tension state during cooldown. Also, specimen distortion evolves during each HF cycle, as the specimen bows downward during HF application and upward during the cooldown period between HF cycles. The final specimen distortion, i.e., upward bowing of the specimen center, was qualitatively predicted for hC values of 4000 to 5000 W/(m 2 ·K). This hC range of values, for which bulging is obtained, is at the lower spectrum of the range of values for hC, consistent with the low thermal contact conductance expected from the unpolished F82H surface.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Transient Microstructure Evolutions and Local Properties of Dual-Phase 980 MPa Grade Steel Via Friction Stir Spot Processing

Friction stir processing is a novel solid-state process to modify microstructures and their properties by intense, localized plastic deformation. However, little research has been reported for microstructure evolutions of advanced high-strength steels during the process. The present work focuses on the study of transient microstructure changes and local mechanical properties for friction stir spot processed dual-phase (DP) 980 MPa grade steel (DP980) under different peak temperatures. A pinless silicon nitride ceramic tool was used to produce relatively simple material deformation and flow near the tool. Friction stir spot processed steel samples were characterized by optical and electron microscopies. Furthermore, Vickers microhardness and nano-indentation measurements were used to study local mechanical properties for correlation with microstructures. A swallow layer of refined grains (<0.6 µm) was obtained with a low peak temperature (under 400 °C), whereas higher peak temperatures (>Ac 1 ) led to a change in grain size with different microstructures (fine-grained DP or martensite). Electron back-scattered diffraction characterizations revealed a large deformation in the as-received microstructures (mixture of ferrite and tempered martensite) induced by friction stir spot processing, leading to recrystallization and grain refinement around the stirred zone. Also, nano-indentation measurements showed a higher hardness than the hardness of the as-received DP980. Friction stir processing with different process conditions effectively changed microstructures and local mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Probing Photoelectrochemical Hydrogen and Oxygen Evolution at Individual Al:SrTiO 3 /Rh 2–y Cr y O 3 Photocatalyst Particles

Particle-based photocatalysts for overall water splitting convert solar energy into hydrogen fuel without the use of any photovoltaic devices. As such they have the potential to revolutionize renewable energy production on Earth. While proven efficiencies have reached 1.1%, further improvements of photocatalyst technology depend on a better understanding of energy loss mechanisms on the individual particle level. Here, we conduct the first in operando photoelectrochemical measurements on individual micrometer-sized Al-doped SrTiO 3 /Rh 2–y CryO 3 photocatalyst particles. We find that the photocatalyst particles behave mainly as water oxidation photoanodes reaching up to 0.5 mA cm −2 at 0.8 V versus RHE and a photovoltage of ∼1.00 V under 4.7 mW cm −2 ultraviolet illumination. This proves that charge separation in the unbiased Al:SrTiO 3 /Rh 2–y Cr y O 3 catalyst is driven by a junction at the n-semiconductor-liquid contact. While O 2 is detected symmetrically around photocatalyst particles, uneven H 2 evolution profiles reflect an irregular Rh 2–y Cr y O 3 cocatalyst distribution. Additionally, the H 2 evolution activity varies significantly between different photocatalyst particles. Furthermore, this suggests that performance gains are possible by better controlling catalyst composition on the microscale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Long-time simulations for fixed input states on quantum hardware

Publicly accessible quantum computers open the exciting possibility of experimental dynamical quantum simulations. While rapidly improving, current devices have short coherence times, restricting the viable circuit depth. Despite these limitations, we demonstrate long-time, high fidelity simulations on current hardware. Specifically, we simulate an XY-model spin chain on Rigetti and IBM quantum computers, maintaining a fidelity over 0.9 for 150 times longer than is possible using the iterated Trotter method. Our simulations use an algorithm we call fixed state Variational Fast Forwarding (fsVFF). Recent work has shown an approximate diagonalization of a short time evolution unitary allows a fixed-depth simulation. fsVFF substantially reduces the required resources by only diagonalizing the energy subspace spanned by the initial state, rather than over the total Hilbert space. We further demonstrate the viability of fsVFF through large numerical simulations, and provide an analysis of the noise resilience and scaling of simulation errors.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

Abstract. Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10−20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Ansatz-Free Hamiltonian Learning with Heisenberg-Limited Scaling

Learning the unknown interactions that govern a quantum system is crucial for quantum information processing, device benchmarking, and quantum sensing. The problem, known as Hamiltonian learning, is well understood under the assumption that interactions are local, but this assumption may not hold for arbitrary Hamiltonians. Previous methods all require high-order inverse polynomial dependency with precision, unable to surpass the standard quantum limit and reach the gold-standard Heisenberg-limited scaling. Whether Heisenberg-limited Hamiltonian learning is possible without prior assumptions about the interaction structures, a challenge we term ansatz-free Hamiltonian learning , remains an open question. In this work, we present a quantum algorithm to learn arbitrary sparse Hamiltonians without any structure constraints using only black-box queries of the system’s real-time evolution and minimal digital controls to attain Heisenberg-limited scaling in estimation error. Our method is also resilient to state-preparation-and-measurement errors, enhancing its practical feasibility. We numerically demonstrate our ansatz-free protocol for learning physical Hamiltonians and validating analog quantum simulations, benchmarking our performance against the state-of-the-art Heisenberg-limited learning approach. Moreover, we establish a fundamental trade-off between total evolution time and quantum control on learning arbitrary interactions, revealing the intrinsic interplay between controllability and total evolution-time complexity for any learning algorithm. These results pave the way for further exploration into Heisenberg-limited Hamiltonian learning in complex quantum systems under minimal assumptions, potentially enabling new benchmarking and verification protocols.

machine learning↗
DOE OSTI2024

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO) 5

Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental–theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin–orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Finally, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Evolution of a Gaussian laser beam in warm collisional magnetoplasma

In this paper, the spatial evolution of an intense circularly polarized Gaussian laser beam propagated through a warm plasma is investigated, taking into account the ponderomotive force, Ohmic heating, external magnetic field, and collisional effects. Using the momentum transfer and energy equations, both modified electron temperature and electron density in plasma are obtained. By introducing the complex dielectric permittivity of warm magnetized plasma and using the complex eikonal function, coupled differential equations for beam width parameter are established and solved numerically. The effects of polarization state of laser and magnetic field on the laser spot size evolution are studied. It is observed that in case of the right-handed polarization, an increase in the value of external magnetic field causes an increase in the strength of the self-focusing, especially in the higher values, and consequently, the self-focusing occurs in shorter distance of propagation. Moreover, the results demonstrate the existence of laser intensity and electron temperature ranges where self-focusing can occur, while the beam diverges outside of these regions; meanwhile, in these intervals, there exists a turning point for each of intensity and temperature in which the self-focusing process has its strongest strength. Finally, it is found that the self-focusing effect can be enhanced by increasing the plasma frequency (plasma density).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

A Stabilized, Intrinsically Safe, 10% Efficient, Solar-Driven Water-Splitting Cell Incorporating Earth-Abundant Electrocatalysts with Steady-State pH Gradients and Product Separation Enabled by a Bipolar Membrane

An efficient, stable, and intrinsically safe solar water-splitting device is illustrated using a III–V tandem junction photoanode, an acid-stable, earth-abundant hydrogen evolution catalyst, and a bipolar membrane. The integrated photoelectrochemical cell operates under a steady-state pH gradient and achieves ≈10% solar-to-hydrogen conversion efficiency, >100 h of stability in a large (>1 cm2) photoactive area in relation to most previous researches.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Role of Innovation in the Electric Utility Sector

Innovation is essential for future power systems to be safe and secure, clean and sustainable, affordable and equitable, and reliable and resilient, according to a recent National Academies report. But state regulatory reforms are needed to encourage adoption of new technologies to support evolution of the nation’s power systems.1 Berkeley Lab's report, The Role of Innovation in the Electric Utility Sector, provides consumer, labor, utility, third-party provider, and clean technology consultant perspectives on this theme. To achieve state targets for clean energy and greenhouse gas emissions, some state regulatory utility commissions are exploring new approaches to spur innovation: -For utilities, regulatory and marketing flexibility, increased funding for demonstration projects, and performance-based ratemaking including multi-year rate plans -For third parties, ways to provide utility customers with innovative products and services directly Among the questions the report addresses: 1. How are consumer advocate views evolving with respect to innovative regulatory and ratemaking approaches? 2. How can utility decarbonization and grid modernization initiatives provide opportunities for local communities and workers to receive tangible benefits and facilitate community support for siting electricity infrastructure? 3. How are electric utilities partnering with technology companies to provide innovative energy management services and sustainable energy solutions for utility customers? 4. What regulatory innovations are public utility commissions exploring to enable third-party providers to participate in the transition to a modern electric system? 5. What regulatory changes are needed to enable innovative solutions from utilities and third parties at the necessary speed and scale to meet state decarbonization goals? The report is the 13th in the Future Electric Utility Regulation series, which taps leading thinkers to tackle complex regulatory issues for electricity. 1 National Academies of Sciences, Engineering, and Medicine. 2021. The Future of Electric Power in the United States. The National Academies Press.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2017

Spectrally resolved localized states in GaAs 1– x Bi x

In this study, the role of localized states and their influence on the broader band structure remains a crucial question in understanding the band structure evolution in GaAs 1-x Bi x . Here in this work, we present clear spectroscopic observations of recombination at several localized states in GaAs 1-x Bi x . Sharp and recognizable photoluminescence features appear in multiple samples and redshift as a function of GaBi fraction between x = 0.16% and 0.4% at a linearized rate of 34 meV per % Bi, weaker than the redshift associated with band-to-band recombination. Interpreting these results in terms of radiative recombination between localized holes and free electrons sheds light on the relative movement of the conduction band minimum and the characteristics of localized bismuth-related trap states in GaAs 1-x Bi x alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Probing autoionizing states of molecular oxygen with XUV transient absorption: Electronic-symmetry-dependent line shapes and laser-induced modifications

In this paper, we used extreme ultraviolet (XUV) transient absorption spectroscopy to study the autoionizing Rydberg states of oxygen in an electronically- and vibrationally-resolved fashion. XUV pulse initiates molecular polarization and near-infrared pulse perturbs its evolution. Transient absorption spectra show positive optical-density (OD) change in the case of $ns{{\sigma}}_{g}$ and $nd{{\pi}}_{g}$ autoionizing states of oxygen and negative OD change for $nd{{\sigma}}_{g}$ states. Multiconfiguration time-dependent Hartree-Fock (MCTDHF) calculations are used to simulate the transient absorption and the resulting spectra and temporal evolution agree with experimental observations. We model the effect of near-infrared perturbation on molecular polarization and find that the laser-induced phase-shift model agrees with the experimental and MCTDHF results, while the laser-induced attenuation model does not. Finally, we relate the electronic-state-symmetry-dependent sign of the OD change to the Fano parameters of the static absorption line shapes.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗
DOE OSTI2026

Concerted Proton–Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis

Molecularly modified electrodes (MMEs) are potent electrocatalysts, but few principles exist for their rational design. Electrocatalysis by soluble molecules depends strongly on substituents that tune the catalyst redox potential (E 1/2 ), but it is unclear if this parameter similarly impacts MME catalysis. Herein, we employ the hydrogen evolution reaction (HER) as a test case for comparing carbon-adsorbed cobalt phthalocyanine (CoPc/C) and cobalt hexadecafluoro-phthalocyanine (CoFPc/C). By correlating HER activity and voltammetric data to total Co surface concentration across a wide range of catalyst loadings, we find that only 5–25% of adsorbed Co sites contribute to the Co(II/I) redox wave and that this subpopulation poorly correlates with catalytic activity. Instead, in the low-loading limit, catalytic activity correlates linearly with the majority Co(II/I)-silent Co population, revealing per-site turnover frequency (TOF) values for HER. Despite a 230 mV difference in Co(II/I) redox potentials, CoPc/C and CoFPc/C display TOF values differing by less than a factor of 3 when compared over a wide potential range. Mechanistic studies point to an inner-sphere concerted proton–electron transfer step as rate-determining, suggesting that the Co–H bond dissociation free energy (BDFE) rather than the Co(II/I) E 1/2 is thermodynamically relevant. Computational studies indicate that the fluoro-substituents lead to compensatory changes in Co(II/I) E 1/2 and Co(I) basicity, leaving the Co–H BDFE largely unchanged between CoPc and CoFPc and thereby manifesting in similar catalytic rates. Furthermore, these results highlight the limited effect of E 1/2 -tuning on MME catalytic activity and motivate the development of methods to directly alter active site–substrate BDFE.

Catalysts↗