Oxygen Atoms Research Articles

Signal oscillations in helium scattering by bismuth atoms in the low energy range

Low Energy Ion Scattering (LEIS) analysis of bismuth selenide (Bi2Se3), a strong 3D topological insulator, revealed oscillations of the detected signal in dependence on primary ion beam energy. Bismuth is a part of the group of elements where oscillatory behaviour was already noticed, such as gallium, indium, or lead. Generally, it is ascribed to quasi-resonant charge exchange processes between primary ion and target atom. Moreover, clear differences exist between data for target atoms in elemental form and for atoms in compound form. A study of Bi signal yields in different material forms was performed for primary He+ projectiles within the energy range from 0.50 to 6.00 keV. A foil of pure Bi, Bi2Se3, Bi2O3 and thin Bi films deposited on several substrates (SiO2, CuOx) by Molecular Beam Epitaxy were analysed. The energy shift in the position of oscillations was observed when the oxygen atoms were present at the surface and bonded to Bi atoms. A description of the Bi ion yield variation is provided to facilitate the quantification process in LEIS.

High-Entropy Lanthanide-Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation.

Multimetallic synergistic effects have the potential to improve CO2 cycloesterification and Knoevenagel reaction processes, outperforming monometallic MOFs. The results demonstrate superior performance in these processes. To investigate this, we created and characterized a selection of single-component Ln(III)-MOFs (Ln = Eu, Tb, Gd, Dy, Ho) and high-entropy lanthanide-organic framework (HE-LnMOF) using solvent-thermal conditions. The experiments revealed that HE-LnMOF exhibited heightened catalytic efficiency in CO2 cycloesterification and Knoevenagel reactions compared to single-component Ln(III) MOFs. Moreover, the HE-LnMOF displayed significant stability, maintaining their structural integrity after five cycles while sustaining elevated conversion and selectivity rates. The feasible mechanisms of catalytic reactions were also discussed. HE-LnMOF possess multiple unsaturated metal centers, acting as Lewis acid sites, with oxygen atoms connecting the metal, and hydroxyl groups on the ligand serving as base sites. This study introduces a novel method for synthesizing HE-LnMOF and presents a fresh application of HE-LnMOF for converting CO2.

Evolution of structure and spectroscopic properties of a new 1,3-diacetylpyrene polymorph with temperature and pressure.

A new polymorph of 1,3-diacetylpyrene has been obtained from its melt and thoroughly characterized using single-crystal X-ray diffraction, steady-state UV-Vis spectroscopy and periodic density functional theory calculations. Experimental studies covered the temperature range from 90 to 390 K and the pressure range from atmospheric to 4.08 GPa. Optimal sample placement in a diamond anvil cell according to our previously presented methodology ensured over 80% data coverage up to 0.8 Å for a monoclinic sample. Unrestrained Hirshfeld atom refinement of the high-pressure crystal structures was successful and anharmonic behavior of carbonyl oxygen atoms was observed. Unlike the previously characterized polymorph, the structure of 2°AP-β is based on infinite π-stacks of antiparallel 2°AP molecules. 2°AP-β displays piezochromism and piezofluorochromism which are directly related to the variation in interplanar distances within the π-stacking. The importance of weak intermolecular interactions is reflected in the substantial negative thermal expansion coefficient of -55.8 (57) MK-1 in the direction of C-H...O interactions.

Creating Atomically Iridium-Doped PdOx Nanoparticles for Efficient and Durable Methane Abatement.

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdOx nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdOx nanoparticles, creating an Ir4f-O-Pdcus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdOx and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir4f-O-Pdcus, reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr0.1/S-1 showed outstanding low-temperature activity for methane combustion (T50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr0.1/S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al2O3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

Atomic-Scale Interface for Pt Nanoparticles on SrTiO3 (001).

The interfacial structure formed by Pt nanoparticles grown epitaxially on a SrTiO3 (001) surface by pulsed laser deposition was studied by X-ray standing-wave (XSW) excited core-level photoelectron emission. The XSW-generated 3D atomic map of the Pt and interfacial oxygens for the oxidized Pt/SrTiO3 interface differs significantly from that of the as-deposited interface. After oxidation, the Pt atoms shifted upward and their atomic occupation at fcc-like sites evolved as the oxidation temperature increased. Interfacial oxygen atoms were differentiated from bulk O atoms by the chemical shift in the binding energy of their 1s electrons. After oxidation, the interfacial oxygen atoms rearranged to form a TiO2 bilayer at the interface. These results provide a more complete description of the strong metal-support interaction process at the interface.

A novel green reducing agent for the synthesis of chromium oxide nanoparticles (Cr2O3 NPs) based on saffron by-products: Characterization and antioxidant activity

The production of nanomaterials using safe, biological and environmentally friendly methods is attracting increasing attention. In the present study, aqueous extracts of Moroccan saffron (Crocus sativus L) by-products were used for the first time as a green stabilizer and reductant agent to synthesize chromium oxide nanoparticles (Cr2O3NPs). The aqueous extract of saffron by-products was analyzed for phytochemical screening, while the green synthesized Cr2O3NPs were analyzed using high-resolution scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The antioxidant activity of Cr2O3NPs, aqueous chromium nitrate solution (Cr (NO3)), and aqueous extract of saffron by-products have been also investigated using 1,1-Diphenyl-2-picrylhydrazyl (DPPH) method. The results showed that the aqueous extract of saffron by-products used for the synthesis of Cr2O3NPs appeared to be rich in phenolic (2.32 mg GA / g dry weight), flavonoid (2.28 mg RE / g dry weight), and anthocyanin compounds (33.67 mg Delphinidin / L extract). The XRD analysis confirmed that the Cr2O3NPs have a particle size of 31 nm with a hexagonal crystal structure. SEM micrographs of Cr2O3NPs showed a homogenous distribution and spherical shape, while the EDX spectrum confirmed that Cr2O3NPs contain significant amount of Chromium (61,90 %), and oxygen atoms (36,55 %). Moreover, the presence of absorption bands characteristic of the alcohol group (3451 cm−1) and the aromatic rings (1639 cm−1) in the infrared spectrum of Cr2O3NPs, indicates that the secondary metabolites of the saffron plant were successfully active in reducing chromium ions to Cr2O3NPs. Besides, the antioxidant activity results showed that the biosynthesized Cr2O3NPs exhibited strong inhibition percentages (63 %) compared to the aqueous extract of saffron by-products (74 %), and the aqueous solution of chromium nitrate (30 %) at 1,30 mg/mL. The study suggests that saffron by-products extract can be used as a natural reducing agent in the synthesis of Cr2O3NPs. Furthermore, the environmentally friendly synthesis process for Cr2O3NPs and their antioxidant effect make them suitable for use in various fields.

Hierarchical porous carbon with abundant N/O doping as an anode for zinc ion hybrid supercapacitors

Aqueous zinc-ion hybrid supercapacitors (ZISCs) known for their affordability, stability, and high energy density represent innovative energy storage devices. Porous carbon is usually used as the cathode material of ZISCs, and its structure significantly affects the dual performance of high power density and energy density of ZISCs. Herein, a one-pot carbonization strategy is proposed, eliminating the need for templates, additional heteroatom compounds, and activation processes. By precisely controlling the temperature to optimize the structure and electrochemical performance of carbon materials, we successfully synthesized hierarchical porous carbon materials (NOPC-800) with a high specific surface area of 1545.7 mg, featuring dual doping of 12.3 at% nitrogen and 13.35 at% oxygen. The self-doping of abundant nitrogen and oxygen atoms facilitates the chemical adsorption of ions and accelerates pseudocapacitive reaction kinetics. Leveraging these advantages, ZISCs were assembled using NOPC-800 as the positive electrode and zinc as the negative electrode, showcasing remarkable performance: a specific capacity of up to 121.9 mAh g, an energy density of 97.5 Wh kg, and a power density of up to 16000 W kg. Remarkably, NOPC-800 maintained an excellent capacity retention of 94.9% after 10,000 cycles at a current density of 10 A g. This research paves an innovative and feasible path for the design and advancement of novel heteroatom-rich carbon cathodes.

Outstanding photocatalytic degradation performance under low light intensity via mitigating the quenching reaction of oxygen-centered organic radicals and oxygen

Traditional indiscriminate free radicals pose challenges to photocatalyst stability. To address this issue, oxygen-centered organic radicals (OCORs) anchored on catalyst surfaces were developed recently. However, strategies to alleviate the quenching reaction between OCORs and oxygen are lacking. Herein, the tetrasubstituted carbazole derivative-anthraquinone CZAQ-1, generating OCORs, was fabricated as photocatalyst. CzAQ-1 outperforms reported photocatalysts under low-intensity visible light, achieving 100 % degradation efficiency within 90 minutes at 10 mW·cm−2 and 30 minutes at 100 mW·cm−2. It exhibits exceptional stability over 10 cycles and yields hydrogen peroxide production of 3582 μmol·h−1·g−1 during degradation. The outstanding performance is attributed to OCORs serving as the primary oxidative active species, effectively mitigating quenching reactions with oxygen. This process is accomplished through an innovative strategy of reducing the electrostatic potential of oxygen atoms in OCORs. This study provides insights into OCORs and proposes strategies for optimizing organic polymer structures to enhance photocatalytic performance by inhibiting OCORs-oxygen reactions.

Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Piroxicam analogue metal complexes: Synthesis, crystal structures, molecular modeling and biological studies

In recent decades, metal‐based drugs have gained considerable attention all over the world because of their enhanced therapeutic potential. The piroxicam analogue, that is, 2‐Benzyl‐4‐hydroxy‐1,1‐dioxo‐1,2‐dihydro‐1λ6‐benzo [e][1,2] thiazine‐3‐carboxylic acid pyridin‐2‐yl amide 1 was synthesized and coupled with Mn (II), Co (II), Ni (II), Cu (II) and Zn (II) metal ions to isolate complexes 2–6. The N,O‐bidentate chelator coordinated with the metal center via pyridyl nitrogen and amide oxygen atoms by forming six‐membered ring system. Several analytical techniques like UV–Vis, FT‐IR, 1H NMR, magnetic susceptibility, and elemental analysis were performed to confirm the syntheses of the octahedral complexes. The conductance measurement was employed to determine the non‐electrolytic nature of the complexes. The molecular structures of manganese (II) 2, cobalt (II) 3, and zinc (II) 6, complexes were confirmed by single beam X‐ray crystallography revealing the monoclinic crystal system with P21/c space group. The crystallographic data was utilized to carry out the DFT studies, which were found in line with the experimental data. The antioxidant (DPPH, FRAP) and antibacterial activities were performed to determine the therapeutic potential of these synthesized compounds. These studies indicated that understudied compounds have potential as therapeutic agents and they may be used as drug candidates in the future. The in‐silico studies also aligned with the in‐vitro potential of the targeted compounds.

Synthesis and Structure of a Coordination Polymer of Ni(II) with 2-(4-Bromophenoxy)acetohydrazide

The coordination compound [NiCl2L(2-PrOH)]n (where L is 2-(4-bromophenoxy)acetohydrazide; 2-PrOH is isopropanol) was obtained for the first time. The complex was characterized by means of elemental analyses, molar conductance, thermogravimetric analysis, IR spectroscopy, and single crystal X-ray diffraction analysis. It was determined that the coordination compound exhibits a polymeric structure. The complexing agent is six-coordinated, and its distorted octahedron forms due to the bidentate coordination of 2-(4-bromophenoxy)acetohydrazide through the carbonyl oxygen atom and the amine nitrogen. The oxygen of the molecule of isopropanol, the chlorine atom, and two chlorine atoms serve as bridges between two metal atoms.

Diamond-like carbon conversion surfaces for space applications

We present diamond-like carbon (DLC) conversion surfaces to detect particles with energy below 2 keV. Conversion surfaces have been widely applied in measurements of low-energy particles by instruments onboard planetary and heliophysics missions. Their effectiveness is characterized by the efficiency in changing the charge state of the incident particles while maintaining a narrow angular distribution for the reflected particles. DLC as a conversion surface coating material has high conversion efficiency. We developed a conversion surface production process that provides ultra-smooth and ultra-thin DLC conversion surfaces. The process includes substrate preparation through precision cleaning, plasma immersion ion deposition of the DLC film, and diagnostics of the film parameters. The latter includes the measurement of the coating thickness, surface roughness, and the conversion efficiency for ion beams with energy below 2 keV. The process we developed provides the DLC conversion surface coating of repeatable parameters with a mean surface roughness of 3.4 ± 0.2 Å and a mean film thickness of 46.7 ± 0.8 nm uniform across the sample area. Ion beam measurements showed a negative ion yield of 1%–2% for hydrogen atoms and 8%–15% for oxygen atoms with an angular scatter distribution of 10°–20° at full width of half maximum. These results agree with those of other conversion surface coatings in the literature. The DLC conversion surfaces presented here are implemented in the conversion surface subsystem of the Interstellar Mapping and Acceleration Probe (IMAP)-Lo instrument of the IMAP mission scheduled for launch in 2025.

Oxygen Atom from Carbonyl Group as an Important Binding Agent to the G-Quadruplex - Study Case of Flavonoids.

In the field of anticancer therapy study it is of great interest to find effective G-quadruplex ligands which may be of potential use in medical treatment or cancer prevention. Since among the compounds of natural origin, flavonoids have attracted notable attention because of their unique properties and promising therapeutic applications, an interesting question was to identify the flavonoid structural features that could provide effective binding properties toward G-quadruplex. By using electrospray ionization mass spectrometry, followed by the survival yield method, it has been shown that the flavonoid molecules which contain an available C4=O carbonyl group form more stable adducts with G-tetrads than the other ones. Molecular docking has shown that C4=O carbonyl group can be a source of hydrogen bonds and/or π-stacking interactions. Therefore, the flavonoid molecules which contain an available C4=O carbonyl group can be regarded as good binders of G-quadruplexes.

Effect of metal doping (M = Sc, V, Ti, Fe and Mn) on the sensing performance of the Si12C12 nanocage towards the penicillamine drug molecule: a DFT study

In this work, we have investigated the electronic properties of the pristine and metal(M)-doped Si12C12 (M = Sc, V, Ti, Fe and Mn) nanocages and their sensing performances towards the penicillamine (PCE) molecule using DFT calculations at the B3LYP/LanL2DZ/6-311G(d,p) method. The results reveal that the doping of the Si12C12 nanocage with a metal atom significantly improves its reactivity, therefore their interaction with the nucleophilic centres of the PCE molecule becomes easy. The most stable complexes were obtained when the PCE molecule was chemisorbed onto the MSi12C12 nanocages through its oxygen atom with adsorption energies which vary from –18.0 to –40.2 kcal mol−1. The results also demonstrate that the MSi12C12 possess high sensitivity towards the PCE molecule. The presence of solvent sharply reduces the adsorption energy of the PCE molecule over the clusters surface, resulting in a substantial decrease in the recovery time. A comparative study between the values of the sensitivity of the studied clusters in liquid phase suggests that the FeSi12C12 and MnSi12C12 clusters present high sensing performances compared with the other clusters, so they are regarded as the best sensors to detect the PCE drug molecule.

Crystal structure and in vitro biological studies of a Pt(II) complex based on gallic acid and triphenylphosphine

Gallic acid is a natural polyphenol found in a variety of fruits, plants and nuts that has several biological properties, such as anti-oxidant, anti-inflammatory, and antitumor, among other activities. Some studies have proven that metal complexation could be an interesting strategy to enhance its pharmacological activities. Taking that into account, we report here the synthesis, spectral characterization (FTIR, 1H, 13C{1H}, 31P{1H} and 195Pt{1H} NMR), structural analysis, and biological activities of a new platinum(II) complex bearing gallic acid (ga) and triphenylphosphine (PPh3) as ligands. Spectral data suggest that a gallic acid molecule chelates the metal via two deprotonated phenolic oxygen atoms and two monodentate triphenylphosphines complete the coordination sphere. Furthermore, X-ray data support that the platinum(II) ion adopts a slightly distorted square-planar coordination environment. Time-dependent 1H NMR spectra at room temperature suggest that the complex is very stable in DMSO for at least 48 h. Subsequently, the cytotoxic activity of the platinum(II) complex was assessed against chronic myelogenous leukemia cells (k562) and in a non-cancerous cell line (LLCMK2). The complex was more active than gallic acid, cisplatin and carboplatin against the K562 cell line, exhibiting outstanding activity (IC50 = 0.75 μM). When tested against Mycobacterium tuberculosis, the complex showed good activity with a MIC value of 3.75 μg/mL. The results reported here reinforce the antitumor and antimycobacterial potential of metal complexes containing gallic acid and derivatives.

A first-principles study of HfB2 anisotropic surface stability and its oxygen adsorption behavior

In this work, the HfB2 anisotropic surface stability, and the adsorption behavior of oxygen molecule on the most likely exposed HfB2 surface were investigated based on density functional theory. The study found that the HfB2(0001) surface terminated by Hf (labeled as: Hf-(0001)) is more stable, and more likely interact with oxygen. By rotating the oxygen molecule orientation and changing the adsorption site, all possible high and low-symmetry adsorption configurations are considered. The results show that the low symmetry structure is unstable, and eventually turn into the high symmetry ones. For the highly symmetric structures, oxygen molecule tends to be adsorbed in parallel, and the dissociated oxygen molecule tends to be located at the bridge and hollow site of the Hf-(0001) surface, and there is no energy barrier to this process. Charge density difference and partial density of states proved that oxygen absorbed structures present similar electronic interaction characteristics, and oxygen adsorption process mainly affects the Hf atom at the outmost layer of the Hf-(0001) plane. Oxygen atoms bind to the Hf-(0001) surface mainly in the form of ionic bonds and covalent bonds, originating from the orbital hybridization of O-p and Hf-d. The oxidation of HfB2 starts from the interaction between oxygen and Hf.

Highly selective and stable electrochemical reduction of nitrate to ammonia using VO2-x/CuF catalyst with oxygen vacancies

Electrocatalytic reduction poses significant challenges due to slow kinetics, limited selectivity, and instability, hindering its potential for sustainable nitrate (NO3−) removal and producing valuable N-containing compounds. This study develops a one-step hydrothermal approach for decorating copper foam (CuF) with VO2 nanobelts. Subsequently, N2 annealing is performed to generate oxygen vacancies (OVs) and yield a VO2-x/CuF sample for its application as an electrocatalyst in reducing NO3− to ammonia (NH3). Several characterization techniques are applied to study the structural and morphological features of the VO2-x/CuF sample, which shows a high crystalline and defective bundle-like structure of nanobelts attributed to the release of oxygen atoms that are beneficial for the electrochemical NO3− reduction processes. The VO2-x/CuF sample demonstrates impressive results, with a NO3− conversion of 78.7 %, an NH4+ yield rate of 1.833 mmol h−1 cm−2, an NH4+ FE of 77.9 %, and a remarkable NH4+ selectivity of 99.7 % at −1.3 V vs RHE. It is worth mentioning that the isotopic labeling findings reveal that the NH4+ originated from NO3− during the electrocatalytic NO3− reduction using a VO2-x/CuF sample. This confinement method effectively creates accessible metallic catalysts with OVs, enabling high-activity, selective and stable NO3− reduction to NH4+ electrocatalysts.

Modified Sodium Alginate for Degradable Supramolecular Plastic with High Mechanical Strength

AbstractPlastic products are widely used in daily life. However, due to the non‐degradability, these plastics pose a great threat to the ecological environment and may even endanger human's health or animal's life. In this paper, we report a degradable and reusable supramolecular plastic. This plastic consists of FeCl3 and polyethylene glycol (PEG) modified sodium alginate (SA). Notably, this plastic exhibits excellent mechanical properties, i. e. it can withstand a load as heavy as 15 kg. This superior mechanical property originates from the double crosslinked network formed based on coordination interaction between Fe3+ and −COOH and hydrogen bonding among −OH, −COOH and oxygen atom from PEG. In addition, this plastic can be reused for multiple times with negligible change in the mechanical strength and is fully degradable. We thus believe the supramolecular plastic reported in the current study may show great promises in the practical fields.

High-energy density cellulose nanofibre supercapacitors enabled by pseudo-solid water molecules

Compared with conventional electrochemical supercapacitors and lithium-ion batteries, the novel amorphous cellulose nanofibre (ACF) supercapacitor demonstrates superior electric storage capacity with a high-power density, owing to its fast-charging capability and high-voltage performance. This study unveils introduces an ACF supercapacitor characterised by a substantial energy density. This is achieved by integrating a singular layer of pseudo-solid water molecules (electrical resistivity of 1.11 × 108 Ω cm) with cellulose nanofibers (CNFs), establishing forming an electric double layer at the electrode interface. The enhanced energy storage in these high-energy density capacitors (8.55 J/m2) is explicated through the polarisation of protons and lone pair electrons on oxygen atoms during water electrolysis, commencing at 1.23 V. Improvements in energy density are attainable through CNF density enhancements and charging-current optimisation. The proposed ACF supercapacitor offers substantial promise for integration into the power sources of flexible and renewable paper-based electronic devices.

Removing the Barrier in O-O Bond Formation Via the Combination of Intramolecular Radical Coupling and the Oxide Relay Mechanism.

The Ru(tda) catalyst has been a major milestone in the development of molecular water oxidation catalysts due to its outstanding performance at neutral pH. The role of the noncoordinating carboxylate group is to act as a nucleophile, donating an oxygen atom to the oxo group, thereby acting as an oxide relay (OR) mechanism for O-O bond formation. A substitution of the carboxylates for phosphonate groups has been proposed, resulting in the Ru(tPaO) catalyst, which has shown even more efficient performance in experimental characterization. In this study, we explore the feasibility of the OR mechanism in the newly reported Ru(tPaO) molecular catalyst. We investigated the catalytic cycle using density functional theory and identified a variation of the OR mechanism that involves radical oxygen atoms in O-O bond formation. We have also determined that the subsequent hydroxide nucleophilic attack is the sole rate-limiting step in the catalytic cycle. All activation free energies are very low, with a free-energy barrier of 2.1 kcal/mol for O-O bond formation and 4.2 kcal/mol for OH- nucleophilic attack.