Activation Barrier Research Articles

Synthesis and structural characterization of picolinamide and thiol chelated Pt(II) complexes: Their kinetics & mechanism and theoretical approach

Picolinamide is a versatile chelating ligand and it reveals peculiar behaviour for metal chelation, particularly for its amide group. The bonding mode of N & O donor centres of an amide group depends on the metal ion, their associated charge and the other associated ligands in metal complexes. Picolinamide (pica) based Pt(II) complex C1 to C4 were synthesized and their bonding mode with Pt(II) was established by different spectroscopic analyses and theoretical approaches for their structural importance and potential anticancer activity. The complex [Pt(pica)Cl2]; C1 was synthesized and its hydrolyzed product [Pt(pica)(OH2)2](ClO4)2; C2 was obtained from hydrolysis of complex C1. The kinetic and mechanistic study for the interaction of complex C2 with l-cysteine (l-cys) and N-acetyl-l-cysteine (N-ac-l-cys) was performed in pseudo-first-order reaction condition to evaluate the rate constants, rate equation, enthalpy of activation (ΔHǂ) and entropy of activation (ΔSǂ). Sulfur chelated complex [Pt(pica)(l-cys)]+; C3 and [Pt(pica)(N-ac-l-cys)]; C4 were obtained when a 1:1 M ratio of C2 and thiol are mixed separately. Theoretical investigation on drug likeness property was evaluated by PASS prediction software. The theoretical approach on structural properties like; structural optimization, HOMO-LUMO energy, TD-DFT simulation, MEP and reactivity descriptors of the complexes were executed and analyzed with the Gaussian09 software package. Molecular docking of the complexes was executed with DNA and BSA.

Reactive molecular dynamics simulations of lithium-ion battery electrolyte degradation

The development of reliable computational methods for novel battery materials has become essential due to the recently intensified research efforts on more sustainable energy storage materials. Here, we use a recently developed framework allowing to consistently incorporate quantum-mechanical activation barriers to classical molecular dynamics simulations to study the reductive solvent decomposition and formation of the solid electrolyte interphase for a graphite/carbonate electrolyte interface. We focus on deriving condensed-phase effective rates based on the elementary gas-phase reduction and decomposition energy barriers. After a short initial transient limited by the elementary barriers, we observe that the effective rate shows a transition to a kinetically slow regime influenced by the changing coordination environment and the ionic fluxes between the bulk electrolyte and the interface. We also discuss the impact of the decomposition on the ionic mobility. Thus, our work shows how elementary first-principles properties can be mechanistically leveraged to provide fundamental insights into electrochemical stability of battery electrolytes.

Structure-Photoreactivity Studies of BODIPY Photocages: Limitations of the Activation Barrier for Optimizing Photoreactions.

BODIPY photocages are photoreactive chromophores that release covalently linked cargo upon absorption of visible light. Here, we used computations of the T1 photoheterolysis barrier to ascertain whether a computational approach could assist in a priori structure design by identifying new structures with higher quantum yields of photorelease. The electronic structure-photoreactivity relationships were elucidated for boron-substituted and core-functionalized 2-substituted BODIPY photocages as well as aryl substitutions at the meso-methyl position. Although there is a clear trend for the 2-substituted derivatives, with donor-substituted derivatives featuring both lower computed barriers and higher experimental quantum yields, no trend in the quantum yield with the computed activation barrier is found for the meso-methyl-substituted or boron-substituted derivatives. The lack of a correlation between the experimental quantum yield with the computed barrier in the latter two substitution cases is attributed to the substituents having larger effects on the rates of competing channels (internal conversion and competitive photoreactions) than on the rate of the photoheterolysis channel. Thus, although in some cases computed photoreaction barriers can aid in identifying structures with higher quantum yields, the ignored impacts of how changing the structure affects the rates of competing photophysical/photochemical channels limit the effectiveness of this single-parameter approach.

Dynamics of Linkers in Metal-Organic Framework Glasses.

Metal-organic framework (MOF) glasses have emerged as a new class of organic-inorganic hybrid glass materials. Considerable efforts have been devoted to unraveling the macroscopic dynamics of MOF glasses by studying their rheological behavior; however, their microscopic dynamics remain unclear. In this work, we studied the effect of vitrification on linker dynamics in ZIF-62 by solid-state 2H nuclear magnetic resonance (NMR) spectroscopy. 2H NMR relaxation analysis provided a detailed picture of the mobility of the ZIF-62 linkers, including local restricted librations and a large-amplitude twist; these details were verified by molecular dynamics. A comparison of ZIF-62 crystals and glasses revealed that vitrification does not drastically affect the fast individual flipping motions with large-amplitude twists, whereas it facilitates slow cooperative large-amplitude twist motions with a decrease in the activation barrier. These observations support the findings of previous studies, indicating that glassy ZIF-62 retains permanent porosity and that short-range disorder exists in the alignment of ligands because of distortion of the coordination angle.

Synthesis of ZnSrP2O7 and CoSrP2O7 Pyrophosphates: Characterization, vibrational properties and electrochemical performance on mild steel in an acidic environment

The pyrophosphates materials present an important performance in the corrosion inhibition field. In the present work, the corrosive behavior of mild steel in a HCl 1 M solution was evaluated in the presence of two pyrophosphates materials CoSrP2O7 and ZnSrP2O7. These inhibitors have been synthesized by solid state method. X-ray diffraction (XRD), Fourier transform infrared analysis (FTIR), Raman spectroscopy, and the scanning electron microscope (SEM) coupled with energy dispersive X-ray (EDX) were provided to characterize the prepared pyrophosphates. The vibrational spectra of the materials were studied in regard to the literature data and upon theoretical group analysis. The inhibiting effect of the two pyrophosphates has been performed using different electrochemical methods, potensiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). As a results, the inhibitors show a mixed-type behavior, in addition to a high corrosion protection with an inhibition efficiency, reach 95.3 % and 89.2 % of CoSrP2O7 and ZnSrP2O7 respectively at 10-3 M. Moreover, the charge transfer resistance (Rct) manifested a notable increase from an initial 34.7 Ω.cm−1 to 598.8 Ω.cm−1 and 224 Ω.cm−1 when CoSrP2O7 and ZnSrP2O7 were introduced respectively. indicating the creation of a protective layer on the surface metal. which was analyzed by SEM-EDX. As for, the thermodynamic parameters such as the entropy, enthalpy and energy of activation have been determined and discussed in the results.

Palladium(II)-catalyzed annulation of N-methoxy amides and arynes: computational mechanistic insights and substituents effects.

The combined use of transition metal-catalyzed C-H activation with aryne annulation reactions has emerged as an important strategy in organic synthesis. In this study, the mechanisms of the palladium(II)-catalyzed annulation reaction of N-methoxy amides and arynes were computationally investigated by density functional theory. The role of methoxy amide as a directing group was elucidated through the calculation of three different pathways for the C-H activation step, showing that the pathway where amide nitrogen acts as a directing group is preferable. At the reductive elimination transition state, an unstable seven-membered ring is formed preventing the lactam formation. A substituent effect study based on an NBO analysis, Hammet, and using a More O'Ferall-Jenks plot indicates that the C-H activation step proceeds via an electrophilic concerted metalation-deprotonation (eCMD) mechanism. The results show that electron-withdrawing groups increase the activation barrier and contribute to an early Pd-C bond formation and a late C-H bond breaking when compared with electron-donating substituents. Our computational results are in agreement with the experimental data provided in the literature. All calculations were performed using Gaussian 16 software. Geometry optimizations, frequency analyses at 393.15 K, and IRC calculations were conducted at the M06L/Def2-SVP level of theory. Corrected electronic energies, NBO charges, and Wiberg bond indexes were computed at the M06L/Def2-TZVP//M06L/Def2-SVP level of theory. Implicit solvent effects were considered in all calculations using the SMD model, with acetonitrile employed as the solvent.

Advanced functional photochromic wearables with fast photo-responsivity, long color-retention, and multi-environmental stability

Smart photochromic wearables have demonstrated attractive prospects in many emerging fields. However, their lower functional performance limits their applications. Herein, we have fabricated a novel photochromic wearable fabric via covalent grafting and chemical isolation technique grafting WO3 nanoflowers onto cellulose. In the charming system, exceptional photochromic properties of WO3 serve as the color-changing material. Besides, incorporated potassium persulfate as a fast-fading reagent is capable of slow oxygen release upon heating. These combined components give the photochromic fabric a rapid response time of 2 s, a fading time of 5 min, and an unprecedented long color-retention (>7 days). Moreover, this photochromic fabric exhibits outstanding rewritability (100 cycles) and exceptional water resistance, maintaining superb photochromic performance even after undergoing standard washing (50 cycles). Moreover, the activation barriers to the photochromic mechanism for the minimum energy pathway were calculated, which provides a theoretical basis for hydrophobic design. The fabric not only imparts water and oil repellence and antifouling properties but also has chemical stability in multi-environments. Notably, the fabrication process is cost-effective, environmentally friendly, and amenable to large-scale production. Such fabrics hold tremendous promise in household products, public facilities and wearable healthcare technologies.

Formation of the oxyl's potential energy surface by the spectral kinetics of a vibrational mode.

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti-O●-) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance-a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode's cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3ps and a time constant of 0.48 ± 0.09ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Fibrinolytic enzyme from Arthrospira platensis: Kinetic and thermodynamic investigation

Fibrinolytic enzymes from microorganisms have been investigated by their potential application as thrombolytic agents. Previous studies show that the fibrinolytic enzyme from Arthrospira platensis (FEAP) is stable at human physiological temperature (<50 °C) and pH (6.0–10.0). Understanding of the kinetic/thermodynamic characteristics is important to make the advances for industrial applications feasible. Therefore, a kinetic/thermodynamic analysis of FEAP was performed on the fibrin hydrolysis and enzyme thermoinactivation. Results showed two Michaelis-Menten-type profiles with two plateaus, revealing high affinity for the substrate with low Michaelis constant values (0.02 and 6.37 µg∙mL−1). The activation energy of the hydrolysis catalyzed by FEAP and the standard enthalpy variations of reversible enzyme unfolding were 49.65 and 107.01 kJ∙mol−1, respectively. When the temperature increased from 40 to 70 °C, the deactivation rate constant increased from 0.0050 to 0.0134 min−1, while the half-life decreased from 138.62 to 51.72 min. These results allowed to estimate the activation energy (E*d = 27.50 kJ∙mol−1), enthalpy (24.64 ≤ ΔH*d ≤ 24.89 kJ∙mol−1), entropy (−209.86 ≤ ΔS*d ≤ −210.10 J∙mol−1∙K−1), and Gibbs free energy (90.61 ≤ ΔG*d ≤ 96.74 kJ∙mol−1) of thermal denaturation. The data suggest that FEAP is a promising and thermostable biocatalyst that could be exploited for industrial applications.

Effects of silanol defects and Ti site location within Ti-MWW on alkene epoxidation with aqueous hydrogen peroxide

Catalytic reaction kinetics and thermodynamics within zeolites respond to the physical properties of the framework through noncovalent interactions with solvents. Here, we demonstrate that rates of alkene epoxidations depend sensitively upon the topological location of Ti atoms and the density of silanol ((SiOH)x) defects in hydrothermally synthesized Ti-MWW catalysts. Turnover rates for 1-hexene epoxidation do not change systematically with (SiOH)x density unlike previous reports for other zeolite framework. Site-averaged turnover rates on Ti-MWW catalysts with the greatest portion of Ti sites located in sinusoidal channels exceed those on materials with most Ti in supercages by a factor of 40-fold. These differences appear to reflect free energy contributions and compensation between activation enthalpies and entropies, induced by the structural organization of solvent molecules that responds differently to the topological locations of active sites and the presence of defects.

Novel synthesis of CuFe2O4/g-C3N4 based on microwave ferromagnetic resonance effect for the thorough removal of TC in mariculture wastewater under natural sunlight

Superior separation of photogenerated carriers holds the key to intensive degradation of tetracycline (TC) in mariculture wastewater under natural sunlight. CuFe2O4/g-C3N4 (CFO/g) was synthesized by secondary microwave co-precipitation (SMCP) based on the ferromagnetic resonance absorption effect. Under the reaction conditions of pH = 6.5, CFO/g = 0.2 g/L, [H2O2] = 1 mM, 99.0 % TC removal was realized in 40 min. Enhanced performance for TC removal in high-salinity environments heavily relied on elevated ionic strength and rapid electron transfer of CFO/g in conjunction with high-salinity interactions. To ecologically remediate mariculture wastewater under natural sunlight, we immobilized powdered CFO/g to a ferrite magnet and devised a continuous flow reaction apparatus, incorporating the controlled injection of hydrogen peroxide (H2O2), to achieve the 100 % TC removal and simultaneously undertake the pretreatment of other contaminants (∼70 %). Ultimately, a safety assessment demonstrated that the degradation of mariculture wastewater by the CFO/g photo-Fenton system is a reliable and efficient technology, and the growth of clownfish remained unimpaired. SMCP successfully accelerated the conversion of high-valent metal ions to low-valent ones and eased the activation barriers of H2O2, enabling various active species to execute their respective roles productively. Innovative application of microwave resonance to enhance the magnetic properties of CFO/g and to support the equilibrium conversion of elemental valence states in high-salinity environments from real wastewater.

Unraveling Hydrogen Adsorption on Transition Metal-Doped [Mo3S13]2- Clusters: Insights from Density Functional Theory Calculations.

Molecular and dissociative hydrogen adsorption of transition metal (TM)-doped [Mo3S13]2- atomic clusters were investigated using density functional theory calculations. The introduced TM dopants form stable bonds with S atoms, preserving the geometric structure. The S-TM-S bridging bond emerges as the most stable configuration. The preferred adsorption sites were found to be influenced by various factors, such as the relative electronegativity, coordination number, and charge of the TM atom. Notably, the presence of these TM atoms remarkably improved the hydrogen adsorption activity. The dissociation of a single hydrogen molecule on TM[Mo3S13]2- clusters (TM = Sc, Cr, Mn, Fe, Co, and Ni) is thermodynamically and kinetically favorable compared to their bare counterparts. The extent of favorability monotonically depends on the TM impurity, with a maximum activation barrier energy ranging from 0.62 to 1.58 eV, lower than that of the bare cluster (1.69 eV). Findings provide insights for experimental research on hydrogen adsorption using TM-doped molybdenum sulfide nanoclusters, with potential applications in the field of hydrogen energy.

Interactions between Cytokines and the Pathogenesis of Prion Diseases: Insights and Implications.

Transmissible Spongiform Encephalopathies (TSEs), including prion diseases such as Bovine Spongiform Encephalopathy (Mad Cow Disease) and variant Creutzfeldt-Jakob Disease, pose unique challenges to the scientific and medical communities due to their infectious nature, neurodegenerative effects, and the absence of a cure. Central to the progression of TSEs is the conversion of the normal cellular prion protein (PrPC) into its infectious scrapie form (PrPSc), leading to neurodegeneration through a complex interplay involving the immune system. This review elucidates the current understanding of the immune response in prion diseases, emphasizing the dual role of the immune system in both propagating and mitigating the disease through mechanisms such as glial activation, cytokine release, and blood-brain barrier dynamics. We highlight the differential cytokine profiles associated with various prion strains and stages of disease, pointing towards the potential for cytokines as biomarkers and therapeutic targets. Immunomodulatory strategies are discussed as promising avenues for mitigating neuroinflammation and delaying disease progression. This comprehensive examination of the immune response in TSEs not only advances our understanding of these enigmatic diseases but also sheds light on broader neuroinflammatory processes, offering hope for future therapeutic interventions.

Remote Activation of H-H Bonds by Platinum in Dilute Alloy Catalysts.

With heterogeneous catalysts, chemical promotion takes place at their surfaces. Even in the case of single-atom alloys, where small quantities of a reactive metal are dispersed within the main host, it is assumed that both elements are exposed and available to bond with the reactants. Here, we show, on the basis of in situ X-ray absorption spectroscopy data, that in alloy catalysts made from Pt highly diluted in Cu the Pt atoms are located at the inner interface between the metal nanoparticles and the silica support instead. Kinetic experiments indicated that these catalysts still display better selectivity for the hydrogenation of unsaturated aldehydes to unsaturated alcohols than the pure metals. Density functional theory calculations corroborated the stability of Pt at the metal-support interface and explained the catalytic performance as being due to a remote lowering of the activation barrier for the dissociation of H2 at Cu sites by the internal Pt atoms.

A Comparison of the Mechanisms and Activation Barriers for Ammonia Synthesis on Metal Nitrides (Ta3N5, Mn6N5, Fe3Mo3N, Co3Mo3N)

In this study we perform a comparison of the reaction mechanism and the activation barrier for the rate-determining step in various metal nitrides (Ta3N5, Mn6N5, Fe3Mo3N, Co3Mo3N) for the ammonia synthesis reaction. The reactions are explained with simplified schematics and the energy profiles for the various reaction mechanisms are given in order to screen the catalytic activity of the catalysts for the ammonia synthesis reaction. We find that the catalytic activity ranks in the following order: Co3Mo3N &gt; Fe3Mo3N &gt; Ta3N5 &gt; Mn6N5. We also find that the reaction mechanism proceeds either by a Langmuir–Hinshelwood and an Eley–Rideal/Mars–van Krevelen mechanism. This is an overview of about 10 years of computational research conducted to provide an overview of the progress established in this field of study.

Coupling electron donors with proton repulsion via Pt-N3-S sites to boost CO2 reduction in CO2/H2 fuel cell

A fuel cell involving CO2/H2 is an appealing energy system to convert CO2 into synthetic fuels as well as to generate electricity using only waste heat. However, overcoming the inherent activation barrier of CO2 to improve the CO2 conversion rate in CO2/H2 fuel cell is still challenging. Herein, we report a synergistic electron-donor and proton-repulsion group composed of Pt-N3-S-C sites to simultaneously modulate the electronic structure and CO2-protonation ability of Ru nanoclusters (RuNC) in RuNC/Pt-N3-S-C catalyst. Experiments combined with theoretical calculations indicate that Pt-N3-S sites not only function as electron donors to Ru nanoclusters to cooperatively induce the orbital hybridization of Ru 3d and the antibonding orbitals of CO2, affording the dissociation of CO bonds in CO2, but also as electronic structure “modulator” to create new active sites on the surface of RuNC to effectively activate molecular CO2. More importantly, an internal polarization field between Pt-N3-S-C and RuNC additionally makes single atom Pt sites repel protons while Ru atoms serve as proton capturers via hydrogen spillover effect, resulting in accelerated protonation of CO2. Consequently, the catalyst exhibits highly improved catalytic activities for CO2 reduction with a conversion rate of 559.1 μmol gcat−1 h−1. This approach helps with fine tuning the electronic structures and catalytic CO2 protonation ability of catalysts for thermal-coupled electrocatalysis.

VT‐NMR Analysis of Rotation‐Inversion of N‐(4‐hydroxybutyl)‐N‐(2,2,2‐trifluoroethyl) tert‐butyl Carbamate: Utilizing the −CH2CF3 Appendage as a Reporter on E/Z‐Isomerization

AbstractThe rotational barrier about the CN carbamate bond of N‐(4‐hydroxybutyl)‐N‐(2,2,2‐trifluoroethyl) tert‐butyl carbamate 1 was determined by variable temperature (VT) 13C and 19F NMR spectroscopy. The −CH2CF3 appendage reports on rotational isomerism and allows for the observation of separate signals for the E‐ and Z‐ensembles at low temperature. The activation barrier for E/Z‐isomerization was quantified using Eyring‐Polanyi theory which requires the measurements of the maximum difference in Larmor frequency Δνmax and the convergence temperature Tc. Both Δνmax and Tc were interpolated by analyzing sigmoidal functions fitted to data describing signal separation and the quality of the superposition of the E‐ and Z‐signals, respectively. Methods for generating the quality‐of‐fit parameters for Lorentzian line shape analysis are discussed. Our best experimental value for the rotational barrier ΔGc≠(1)=15.65±0.13 kcal/mol is compared to results of a higher level ab initio study of the model N‐ethyl‐N‐(2,2,2‐trifluoroethyl) methyl carbamate.

Enhancing the catalytic activity of Pd nanoparticles in the hydrolysis of ethylenediamine-bisborane through sulfonation of graphene oxide as a solid support

Ethylenediamine-bisborane (EDB), with its high hydrogen storage capacity, has been in the limelight among researchers. In this study, a new catalytic hybrid material (Pd@rGO-SO3H), comprising sulfonated reduced graphene oxide (rGO-SO3H) and palladium (Pd), was developed. This material serves as a highly efficient and reusable catalyst in the hydrogen production from EDB hydrolysis. The synthesized EDB, rGO-SO3H, and Pd@rGO-SO3H were characterized using ICP-OES, PXRD, XPS, SEM, TEM, and TEM/EDX tools. The initial TOF value of the Pd@rGO-SO3H catalyst in hydrogen production from EDB hydrolysis was calculated as 136 min−1. This TOF value was found to be remarkably high compared to related studies in the literature. The reusability performance of Pd@rGO-SO3H was observed to be quite stable. Finally, activation parameters, such as activation energy (Ea), activation enthalpy (ΔH#), and activation entropy (ΔS#) for the hydrolysis reaction, were calculated by conducting catalytic reactions at different temperatures using relevant equations.

Generation of High-Lying Vibrational States in Carbon Dioxide through Coherent Ladder Climbing.

Mid-infrared laser excitation of molecules into high-lying vibrational states offers a novel route to realize controlled ground-state chemistry. Here we successfully demonstrate vibrational ladder climbing in the antisymmetric stretch of CO2 in the condensed phase by using intense down-chirped mid-infrared pulses. Spectrally resolved pump-probe measurements directly observe excited-state absorptions attributed to vibrational populations up to the v = 9 state, whose corresponding energy of 2.5 eV is 46% of the dissociation energy. By the use of global fitting analysis, important spectroscopic parameters in the high-lying vibrational states, such as transition frequencies and relaxation times, are quantitatively characterized. Remarkably, our analysis shows that 40% of the molecules are excited above the typical activation barriers in the metal-catalyzed CO2 conversions. These results not only demonstrate the promising ability of infrared excitation to produce elevated vibrational states but also represent a significant step toward accelerating CO2 conversions and other chemical processes via mode-specific vibrational excitation.

Mitigating the Jahn–Teller effect and enhancing the conductivity of O3-type NaNi1/3Fe1/3Mn1/3O2 cathode through Mn replacement with Sc for high-performance sodium-ion batteries

This study presents a novel modification strategy involving the replacement of Mn with Sc in the cathode of NaNi1/3Fe1/3Mn1/3O2 (NFM). The results of this study confirmed that Sc doping introduced strong Sc–O bonds to enhance the bonding between transition metal ions and O2−. Additionally, Sc doping reduced the proportion Mn3+ in the material (from 50.23% to 47.46%), thereby inhibiting the material structural distortion due to the Jahn–Teller effect induced by Mn3+. These factors were the main contributors to the improved cycling performance of the modified material. Furthermore, the introduction of Sc decreased the band gap of the material (1.7416–1.6706 eV) and the Na+ activation barrier energy (0.773–0.732 eV). These changes not noly facilitated the de-embedding of Na+ in the material lattice but also significantly enhanced the material electronic conductivity, leading to an excellent rate performance of the modified material. These results indicate that the NFM-Sc0.01 sample maintained an ultra-high capacity retention of 86.45% after 200 cycles at 1 C. At 5 C, the discharge capacity of NFM-Sc0.01 significantly increased from 79.3 mAh g−1 in NFM to 93.4 mAh g−1, demonstrating great potential for industrialized applications.