Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Intact”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Expression Patterns of Energy-Related Genes in Single Cells Uncover Key Isoforms and Enzymes That Gain Priority Under Nanoparticle-Induced Stress

Cellular responses to nanoparticles (NPs) have been largely studied in cell populations, providing averaged values that often misrepresent the true molecular processes that occur in the individual cell. To understand how a cell redistributes limited molecular resources to achieve optimal response and survival requires single-cell analysis. Here we applied multiplex single molecule-based fluorescence in situ hybridization (fliFISH) to quantify the expression of 10 genes simultaneously in individual intact cells, including glycolysis and glucose transporter genes, which are critical for restoring and maintaining energy balance. We focused on individual gill epithelial cell responses to lithium cobalt oxide (LCO) NPs, which are actively pursued as cathode materials in lithium-ion batteries, raising concerns about their impact on the environment and human health. We found large variabilities in the expression levels of all genes between neighboring cells under the same exposure conditions, from only a few transcripts to over 100 copies in individual cells. Gene expression ratios among the 10 genes in each cell uncovered shifts in favor of genes that play key roles in restoring and maintaining energy balance. Among these genes are isoforms that can secure and increase glycolysis rates more efficiently, as well as genes with multiple cellular functions, in addition to glycolysis, including DNA repair, regulation of gene expression, cell cycle progression, and proliferation. Our study uncovered prioritization of gene expression in individual cells for restoring energy balance under LCO NP exposures. Broadly, our study gained insight into single-cell strategies for redistributing limited resources to achieve optimal response and survival under stress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Role of the Mineral in the Self-Healing of Cracks in Human Enamel

Human enamel is an incredibly resilient biological material, withstanding repeated daily stresses for decades. The mechanisms behind this resilience remain an open question, with recent studies demonstrating a crack-deflection mechanism contributing to enamel toughness and other studies detailing the roles of the organic matrix and remineralization. Here, we focus on the mineral and hypothesize that self-healing of cracks in enamel nanocrystals may be an additional mechanism acting to prevent catastrophic failure. To test this hypothesis, we used a molecular dynamics (MD) approach to compare the fracture behavior of hydroxyapatite (HAP) and calcite, the main minerals in human enamel and sea urchin teeth, respectively. In this work, we find that cracks heal under pressures typical of mastication by fusion of crystals in HAP but not in calcite, which is consistent with the resilience of HAP enamel that calcite teeth lack. Scanning transmission electron microscopy (STEM) images of structurally intact ("sound") human enamel show dashed-line nanocracks that resemble and therefore might be the cracks healed by fusion of crystals produced in silico . The fast, self-healing mechanism shown here is common in soft materials and ceramics but has not been observed in single crystalline materials at room temperature. The crack self-healing in sound enamel nanocrystals, therefore, is unique in the human body and unique in materials science, with potential applications in designing bioinspired materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single-Phase Spinel NiCo 2 O 4 as Highly Active and Stable Electrocatalysts for Urea Oxidation Reaction in Urea Electrolysis

Exploring and designing a stable and active catalyst for the urea electro-oxidation reaction (UOR, CO(NH 2 ) 2 + 6OH – → CO 2 + N 2 + 5H 2 O + 6e – ) is crucial for the long-term sustainability of ecological systems and clean energy production. We found that spinel NiCo 2 O 4 is a stable and active electrocatalyst for UOR at a relatively low anodic potential without triggering the competing oxygen evolution reaction (OER). A urea electrolysis cell (CO(NH 2 )2 + H 2 O → CO 2 + N 2 + 2H 2 ) utilizing a spinel NiCo 2 O 4 anode and a commercial Pt cathode was further characterized through galvanostatic polarization tests, demonstrating excellent structural stability at various current densities. Post-mortem analysis of long-term urea electrolysis measurements suggested that NiCo 2 O 4 electrocatalysts maintained a stable spinel structure. However, redistribution of Ni 3+ to Ni 2+ valence on the catalyst surface was observed, in contrast to the intact Co valence, indicating that (i) Ni sites are active toward urea adsorption and sequential electro-oxidation; (ii) while urea oxidation proceeds primarily through the direct electro-oxidation mechanism, chemical reactions between the Ni 3+ site and urea occur during long-term electrochemical UOR operation. Density functional theory (DFT) simulations were used to calculate the adsorption energies of urea molecules on NiO, Co 3 O 4 , and NiCo 2 O 4 , revealing the importance of regulating the configuration of adsorbed urea molecules on the NiCo 2 O 4 surface.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Significance of a Solid Electrolyte Interphase on Separation of Anode and Cathode Materials from Spent Li-Ion Batteries by Froth Flotation

The separation of electrode active materials from spent Li-ion batteries (LIBs) by froth flotation is challenging due to the changes in surface properties of electrode active materials from cycling as well as the presence of organic binders. In this work, the froth flotation separation of aged anode and cathode composite materials from spent LIBs was systematically investigated after the materials were heat treated. The results show that aged anode and cathode materials from spent LIBs can be well separated from each other after a heating process in air at 400 degrees C and at which some of the PVDF binder remains intact. The underlying mechanism was investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurements, and scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX). The results from the XPS and contact angle measurements show that there is a hydrophilic and oxygen-rich layer on the surface of aged anode materials. This hydrophilic surface, associated with the solid electrolyte interface (SEI) layer, impacts the froth flotation process significantly. The results also show that both the SEI layers and PVDF binder residues on the surface are removed at 400 degrees C for an hour, restoring the hydrophobicity of the anode materials, which, in turn, benefits the separation of anode and cathode materials. The STEM/EDX elemental analysis data confirms that there are 20 nm-thick oxygen-rich SEI layers on the surfaces, which can be removed after a heating process. The present result illustrates the significance of the SEI layers in flotation separation of electrode materials and sheds new lights into the future development of the recycling processes for the separation of anode and cathode composite materials from spent Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Low Field NMR Relaxometry Characterization of Water Adsorption in Corn Stover Anatomical Fractions

Low magnetic field 2 MHz NMR relaxometry is applied to measure water adsorption processes of intact corn stover anatomical fractions. Comparison with high magnetic field 250 MHz relaxometry of milled corn stover fractions as a function of water activity, i.e., relative humidity, provides insight into the microstructural changes of the biomass and varying water molecular dynamics during adsorption. As a result, the data presented establish a basis for low field portable NMR of biomass in situ in field and processing environments.

09 BIOMASS FUELS↗
DOE OSTI2026

Delamination of Multilayer Plastic Films to Recover Polyethylene with Favorable Mechanical Properties

Multilayer plastic films play a critical role in packaging, with each polymer layer contributing specific properties to the multilayer film. Multilayer plastic films are not currently recyclable due to the bound polymers. With multilayer film production of about 20 million metric tons in 2024 and rising, endof- life treatment becomes pressing. This work presents a scalable solvent-based delamination recycling process that is applied to commercial postindustrial multimaterial films to unbind the materials within a multilayer film by dissolving only the adhesive layer and recover polyethylene (PE) as an intact solid film. Solventbased delamination is a simple process that allows the complete recovery of materials and solvents used in the process. The delaminating solvent, 88% formic acid in water, induces delamination of PE/PEI/PET and PE/PU/PET films at 70 °C in under an hour. Recovered PE has no contamination detected by Fourier transform infrared spectroscopy and mechanical properties on par with those of virgin resin. The recovery of high-quality solid PE film fit for reprocessing, at low operating temperatures and with closed-loop solvent reuse, promotes delamination as a low energy consumption and environmentally friendly recycling process. PE recovered from delamination can be reused in equivalent products, promoting circularity of multimaterial films.

chemical recycling↗
DOE OSTI2018

Metal–Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

A chemically and thermally stable, mesoporous, crystalline metal–organic framework, NU-1000, serves as a structurally well-defined support for catalytic reactions. Depositing chromium(III), a metal widely used in homogeneous ethylene oligomerization catalysts, onto the Zr6 node of NU-1000 allows for the atomically precise determination of the structure of the Cr3+ catalyst through single-crystal X-ray diffraction studies. Chromium modification of NU-1000 was accomplished via solvothermal deposition in MOFs (SIM); termed Cr-SIM-NU-1000, the elaborated material features individual Cr atoms directed in single-site fashion into the mesopore of NU-1000. It was found that NU-1000 serves to stabilize the catalyst against both the typical chemical deactivation of homogeneous systems and leaching from heterogeneous systems. Cr-SIM-NU-1000 exhibits superior catalytic activity, as compared to Cr2O3, for ethylene oligomerization, with 20% conversion at a turnover frequency of about 60 h–1 and products ranging from C8–C28. Given that this catalysis occurs at low temperature (ambient) and low pressure (1 bar C2H4), along with minimal quantity of cocatalyst, the high activity shown by Cr-SIM-NU-1000 enables significant reduction in materials usage and waste. Postcatalytic characterization reveals Cr-SIM-NU-1000 remains intact with no leaching under the reaction conditions.

catalysis (heterogeneous), materials and chemistry↗
DOE OSTI2025

Robust Synthetic Biology Toolkit to Advance Carboxysome Study and Redesign

Carboxysomes are polyhedral protein organelles that microorganisms use to facilitate carbon dioxide assimilation. They are composed of a modular protein shell that envelops an enzymatic core mainly composed of physically coupled Rubisco and carbonic anhydrase. While the modular construction principles of carboxysomes make them attractive targets as customizable metabolic platforms, their size and complexity can be a hindrance. In this work, we design and validate a plasmid set, the pXpressome toolkit, in which α-carboxysomes are robustly expressed and remain intact and functional after purification. We tested this toolkit by introducing mutations that influence carboxysome structure and performance. We find that deletion of vertex-capping genes results in formation of larger carboxysomes, while deletion of facet forming genes produces smaller particles, suggesting that adjusting the ratio of these proteins can rationally affect morphology. Through a series of fluorescently labeled constructs, we observe that this toolkit leads to more uniform expression and better cell health than previously published carboxysome expression systems. Overall, the pXpressome toolkit facilitates the study and redesign of carboxysomes with robust performance and improved phenotype uniformity. The pXpressome toolkit will support efforts to remodel carboxysomes for enhanced carbon fixation or serve as a platform for other nanoencapsulation goals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Engineering the S-Layer of Caulobacter crescentus as a Foundation for Stable, High-Density, 2D Living Materials

Materials synthesized by organisms, such as bones and wood, combine the ability to self-repair with remarkable mechanical properties. This multifunctionality arises from the presence of living cells within the material and hierarchical assembly of different components across nanometer to micron scales. While creating engineered analogs of these natural materials is of growing interest, our ability to hierarchically order materials using living cells largely relies on engineered 1D protein filaments. Here, we lay the foundations for bottom-up assembly of engineered living material composites in 2D along the cell body using a synthetic biology approach. We engineer the paracrystalline surface-layer (S-layer) of Caulobacter crescentus to display SpyTag peptides that form irreversible isopeptide bonds to SpyCatcher-modified proteins, nanocrystals, and biopolymers on the extracellular surface. Using flow cytometry and confocal microscopy, we show that attachment of these materials to the cell surface is uniform, specific, and covalent, and its density can be controlled based on the location of the insertion within the S-layer protein, RsaA. Furthermore, we leverage the irreversible nature of this attachment to demonstrate via SDS-PAGE that the engineered S-layer can display a high density of materials, reaching 1 attachment site per 288 nm 2 . Lastly, we show that ligation of quantum dots to the cell surface does not impair cell viability and this composite material remains intact over a period of two weeks. Taken together, this work provides a platform for self-organization of soft and hard nanomaterials on a cell surface with precise control over 2D density, composition, and stability of the resulting composite, and is a key step towards building hierarchically-ordered engineered living materials with emergent properties.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Structural Characterization of a Synthetic Tandem-Domain Bacterial Microcompartment Shell Protein Capable of Forming Icosahedral Shell Assemblies

Bacterial microcompartments are subcellular compartments found in many prokaryotes; they consist of a protein shell that encapsulates enzymes that perform a variety of functions. The shell protects the cell from potentially toxic intermediates and co-localizes enzymes for higher efficiency. Accordingly, it is of considerable interest for biotechnological applications. We have previously structurally characterized an intact 40 nm shell comprised of three different types of proteins. One of those proteins, BMC-H, forms a cyclic hexamer; here we have engineered a synthetic protein that consists of a tandem duplication of BMC-H connected by a short linker. The synthetic protein forms cyclic trimers that self-assemble to form a smaller (25 nm) icosahedral shell with gaps at the pentamer positions. When co-expressed in vivo with the pentamer fused to an affinity tag we can purify complete icosahedral shells. This engineered shell protein constitutes a minimal shell system to study permeability; reducing symmetry from six- to three-fold will allow for finer control of the pore environment. In conclusion, we have determined a crystal structure of this shell to guide rational engineering of this microcompartment shell for biotechnological applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Diffractive Imaging of Conical Intersections Amplified by Resonant Infrared Fields

The fate of virtually all photochemical reactions is determined by conical intersections. These are energetically degenerate regions of molecular potential energy surfaces that strongly couple electronic states, thereby enabling fast relaxation channels. Their direct spectroscopic detection relies on weak features that are often buried beneath stronger, less interesting contributions. For azobenzene photoisomerization, a textbook photochemical reaction, we demonstrate how a resonant infrared field can be employed during the conical intersection passage to significantly enhance its coherence signatures in time-resolved Xray diffraction while leaving the product yield intact. Furthermore, this transition-state amplification holds promise to bring signals of conical intersections above the detection threshold.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interzeolite Transformation through Cross-Nucleation: A Molecular Mechanism for Seed-Assisted Synthesis

Polymorph selection and efficient crystallization are central goals in zeolite synthesis. Crystalline seeds are used for both purposes. While it has been proposed that zeolite seeds induce interzeolite transformation by dissolving into structural units that promote nucleation of the daughter crystal, the seed’s structural elements do not always match those of the target zeolite. This discrepancy raises the question of how the seed promotes the daughter phase. Here, we present the first molecularly resolved investigation of seed-assisted zeolite synthesis. Using molecular simulations, we reproduce the experimental finding that a parent zeolite can promote the nucleation of a daughter zeolite even when it lacks common composite building units (CBUs) or crystal planes. Modeling the seed-assisted synthesis of an AFI-type zeolite using zeolite CHA, our simulations indicate that stand-alone CBUs from the parent seed do not facilitate daughter crystal formation. However, introducing the intact seed significantly reduces the synthesis time, supporting that seed integrity is key to increased efficiency. This reduction arises from the cross-nucleation of the AFI-type zeolite on the CHA (001) face. We find that parent and daughter zeolites are connected by an interfacial transition layer with an order distinct from that of both zeolites. Simulations reveal that cross-nucleation occurs over a broad range of synthesis conditions. We argue that cross-nucleation would be most favorable for zeolite pairs that share crystalline planes such as those forming intergrowths. In conclusion, our findings suggest that the prevalence of intergrowths with a common lattice plane in zeolite synthesis is likely a kinetic effect of accelerated cross-nucleation.

Crystallization↗
DOE OSTI2025

Defect-Driven Redox Interplay on Anatase TiO 2 : Surface-Structure Dependent Activation for CO 2 Hydrogenation Catalysis

Titanium dioxide (TiO 2 ) is one of the most extensively studied oxides as an active catalyst or catalyst support, particularly in energy and environmental applications, but the atomistic mechanisms governing its dynamic response to reactive environments and their correlation to reactivity remain largely elusive. Using in situ environmental transmission electron microscopy (ETEM), synchrotron X-ray diffraction (XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), temperature-programmed reduction (TPR), reactivity measurements, and theoretical modeling, we reveal the dynamic interplay between oxygen loss and replenishment of anatase TiO 2 under varying reactive conditions. Under H 2 exposure, anatase TiO 2 undergoes surface reduction via lattice oxygen loss, forming Ti 3 O 5 . In contrast, CO 2 exposure induces oxygen replenishment, reversing stoichiometry. In mixed H2/CO 2 environments, the reverse water–gas shift (RWGS) reaction proceeds selectively on stepped and high-indexed TiO 2 surfaces, whereas the thermodynamically stable TiO 2 (101) surface remains inactive and intact. Critically, H 2 pretreatment generates oxygen vacancies on TiO 2 (101), transforming it into an active Ti 3 O 5 or defect-rich surface that catalyzes RWGS. By correlating surface structure, defect dynamics, and gas-phase interactions, this work deciphers the competition between H 2 -driven reduction and CO 2 -driven oxidation pathways at the atomic scale. Furthermore, these insights establish defect engineering as a strategic lever to activate inert TiO 2 facets, advancing the design of adaptive catalysts for sustainable fuel synthesis technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic Studies of Oxidative Degradation in Diamine-Appended Metal–Organic Frameworks Exhibiting Cooperative CO 2 Capture

Understanding the impact of O 2 during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O 2 -induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O 2 -induced degradation of diamine-appended metal−organic frameworks (MOFs) exhibiting cooperative CO 2 adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2−Mg 2 (dobpdc) (e-2 = N-ethylethylenediamine, dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), under various temperatures and O 2 pressures. These experiments show that diamine degradation inhibits CO 2 chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O 2 exposure. Detailed characterization of O 2 -exposed e-2−Mg 2 (dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C−N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH • , (ii) carbon-centered radicals generated via radical transfer reactions react with O 2 , leading to amine degradation, and (iii) the ratelimiting step of the degradation reactions likely involves O−O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O 2 -induced amine degradation in next-generation carbon capture technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Native Architecture of Wheat Straw Cell Walls: A Unified Model from X-ray Scattering and Solid-State NMR

Plant secondary cell walls constitute the dominant reservoir of renewable biomass, comprising tightly packed cellulose, hemicellulose, and lignin at the nanoscale. Recent advances in solid-state NMR spectroscopy and the availability of small-angle X-ray scattering for biomass characterization have led to an accumulation of experimental data on cell wall organization, yet no explicit structure model has simultaneously satisfied both Xray and NMR observations. Using wheat straw as a model system, we propose a structural framework consistent with current knowledge of cellulose biosynthesis, X-ray scattering data, and one- and two-dimensional 13 C solid-state NMR spectra. In this model, 18-chain elementary fibrils align in parallel and populate the cross-section at random. Arabinose-substituted xylan shows no conformational dependence for cellulose-binding in wheat, and only a minor fraction of 2-fold xylan appears in close proximity to cellulose, unlike in Arabidopsis, where xylan is more tightly attached to the cellulose surface. While NMR data cannot unambiguously resolve the internal arrangement of the 18 glucan chains, X-ray scattering profiles uniquely constrain the fibril size and exclude the possibility of tight bundling in the intact walls. The specific interaction between the matrix polymers and the cellulose elementary fibrils must be reconsidered in light of the small interfibril spaces, which bring the matrix components into spatial proximity with cellulose even in the absence of attractive interactions. These findings provide fundamental molecular-level insight into cellulose fibril architecture and matrix−polymer interactions, resolving longstanding discrepancies between spectroscopic and scattering data and advancing our understanding of biopolymer assembly into structurally and functionally versatile lignocellulosic biomaterials.

Carbohydrates↗
DOE OSTI2019

Mechanism of Inactivation of Ornithine Aminotransferase by (1S,3S)-3-Amino-4-(hexafluoropropan-2-ylidenyl)cyclopentane-1-carboxylic Acid

The inhibition of ornithine aminotransferase (OAT), a pyridoxal 5'-phosphate-dependent enzyme, has been implicated as a treatment for hepatocellular carcinoma (HCC), the most common form of liver cancer, for which there is no effective treatment. From a previous evaluation of our aminotransferase inhibitors, (1S,3S)-3-amino-4-(perfluoropropan-2-ylidene)cyclopentane-1-carboxylic acid hydrochloride (1) was found to be a selective and potent inactivator of human OAT (hOAT), which inhibited the growth of HCC in athymic mice implanted with human-derived HCC, even at a dose of 0.1 mg/kg. Currently, investigational new drug (IND)-enabling studies with 1 are underway. The inactivation mechanism of 1, however, has proved to be elusive. In this work we propose three possible mechanisms, based on mechanisms of known aminotransferase inactivators: Michael addition, enamine addition, and fluoride ion elimination followed by conjugate addition. On the basis of crystallography and intact protein mass spectrometry, it was determined that 1 inactivates hOAT through fluoride ion elimination to an activated 1,1'-difluoroolefin, followed by conjugate addition and hydrolysis. This result was confirmed with additional studies, including the detection of the cofactor structure by mass spectrometry and through the identification of turnover metabolites. On the basis of this inactivation mechanism and to provide further evidence for the mechanism, analogues of 1 (19, 20) were designed, synthesized, and demonstrated to have the predicted selective inactivation mechanism. These analogues highlight the importance of the trifluoromethyl group and provide a basis for future inactivator design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A Robust Methodology to Elucidate Kinetics of Room Temperature Electrochemical Propane Adsorption on Platinum

Electrocatalytic activation of alkanes can further decarbonize chemical manufacturing by leveraging affordable renewable electricity and readily available shale gas reserves in the United States. Earlier works have identified the unique role of Pt in adsorbing and activating alkanes, like propane, at room temperature in acidic, aqueous electrolytes, revealing spontaneous formation of deeply dehydrogenated propane-derived surface species with an intact C 3 - backbone. Although an adsorption mechanism was hypothesized, it has not been explicitly investigated to date, preventing the quantification of kinetic rate parameters. A robust methodology to investigate and benchmark propane adsorption kinetics on Pt is critical for the rational design of electrocatalysts that exhibit higher selectivity toward desired partially oxidized products. Herein, we analyze an oxidative current transience that appears during the adsorption of propane on Pt in aqueous electrochemical conditions and develop a methodology that elucidates the adsorption mechanism and enables quantification of rate parameters such as order dependences and apparent activation barriers. This method yields an expected first-order dependence with respect to propane concentration at low coverage and reveals a second-order dependence with respect to the concentration of surface active sites. Additionally, the apparent activation barrier for propane adsorption was calculated using an Arrhenius analysis of the current transience under temperature control. The experimentally measured activation barrier of 35 kJ mol –1 is in excellent agreement with the theoretical barrier calculated by density functional theory (DFT). The kinetic analysis was extended, via the use of transition state theory, to extract entropy and enthalpy of activation, yielding consistent results with the proposed two-step adsorption mechanism and DFT calculations. These results demonstrate reliable quantification of kinetic parameters for electrocatalytic activation of C–H bonds in alkanes that can be employed for rational catalyst development for a versatile range of electrocatalytic conditions.

alkane activation↗