Oxide Anion Research Articles

Heteroatom Effect on Site-Selective Oxygen-Sulfur Substitution Reactions of Keggin-Type Polyoxotungstates.

Sulfur, a group 16 element, can substitute the oxygen sites of metal oxides, potentially providing them with unique properties and enabling new applications. Polyoxometalates (POMs) are anionic metal oxide clusters with wide structural diversity owing to arbitrary selection of their constituting metal atoms. However, substitution of the oxygen sites of POMs with sulfur atoms has been rarely explored. Recently, we reacted a Keggin-type POM [XW12O40]4- (IX; X = Si and Ge) with a sulfurizing reagent (Lawesson's reagent), synthesizing Keggin-type polyoxothiometalates (POTMs) [XW12O28S12]4- (IIX, X = Si and Ge) in which all 12 terminal oxygen atoms of IX were site-selectively substituted with sulfur atoms. Although the selected heteroatoms (X) and anion charges substantially influence the properties and reactivities of POMs, oxygen-sulfur substitution of Keggin-type POMs with other heteroatoms and anion charges has not been attempted. Herein, we report the oxygen-sulfur substitution reaction of Keggin-type POMs [XW12O40]n- (IX; X = Al, Si, and P; n = 5, 4, and 3, respectively) with various heteroatoms, yielding the corresponding Keggin-type POTMs [XW12O28S12]n- (IIX). The oxygen-sulfur substitution reaction depended on the heteroatom: POMs with higher anion charges reacted more strongly with the sulfurizing reagents. We also investigated the reaction mechanism of POMs and sulfurizing reagents.

Photocatalyzed oxidation of water on oxygen pretreated rutile TiO2(110)

The oxygen evolution reaction (OER) is the bottleneck in the overall photocatalytic splitting of water. The active sites (terminal titanium or bridging oxygen) and active species (molecular or dissociative water) of the initial step of the photocatalyzed OER on the prototypical photocatalyst TiO2, remain debatable. Herein, the photocatalytic chemistry of monolayer water on oxygen-pretreated TiO2(110) (o-TiO2(110)) and reduced TiO2(110) (r-TiO2(110)) surfaces initiated by 400 nm light illumination was investigated by time-dependent two-photon photoemission spectroscopy (TD-2PPE). The photoinduced reduction of the H2O/o-TiO2(110) interface rather than the H2O/r-TiO2(110) interface was detected by TD-2PPE. The difference in 2PPE originated from the presence of the terminal hydroxyl anions (OHt¯) on H2O/o-TiO2(110), as identified by X-ray photoelectron spectroscopy and temperature-programmed desorption. Therefore, the evolution of the electronic structure of H2O/o-TiO2(110) was attributed to the photocatalyzed oxidation of the terminal hydroxyl anions, which most likely formed gaseous •OH radicals, reducing the interface. This work suggested that the oxidation of hydroxyl anions on top of the terminal titanium ions on TiO2, which were excluded previously in solution, need to be considered in the mechanistic studies of the photocatalyzed OER.

Effect of 5β-dihydrotestosterone on vasodilator function and on cell proliferation.

Aging is one of the main factors associated with cardiovascular diseases. Androgens exert beneficial effects on the cardiovascular system and testosterone (TES) replacement therapy improves cardiometabolic risk factors. However, TES is contraindicated in patients with prostate cancer due to its proliferative effects on prostatic tumor cells. Additionally, TES and its reduced metabolites 5α- and 5β-dihydrotestosterone (5α-DHT and 5β-DHT) exert vasodilatory effects. Since androgen levels decrease during aging and 5β-DHT lacks genomic effects, this study is focused on analyzing its effect on vasodilator function and the proliferation rate of prostatic tumor and vascular smooth muscle cells. To study the vascular function, mesenteric arteries from aged-orchidectomized Sprague-Dawley rats were used. Mesenteric segments were divided into one control (without treatment) and three groups with the androgens (10 nM, 30 min) to analyze: acetylcholine- and sodium nitroprusside-induced responses and nitric oxide and superoxide anion production. To analyze cell proliferation, the effect of androgens on cell viability was determined. The results showed that 5β-DHT improves vasodilator function in arteries from aged-orchidectomized rats and induces antioxidant action, while the proliferation rate of the androgen-dependent prostatic tumor cells remains unaltered. These results make 5β-DHT a promising therapeutic agent for the treatment of cardiovascular pathologies.

Design of a bifunctional prepolymer for simultaneously facile preparation and highly efficient electrodialysis of anion exchange membranes

A facile fabrication process for separation membranes is crucial to decrease the production cost, while the photo-polymerization approach can be conducted at ambient conditions with short processing time and low energy consumption. Herein, this work designs a bifunctional prepolymer for simultaneously facile preparation and highly efficient electrodialysis of poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) anion exchange membranes. PPO is selected as the main skeleton of prepolymer because of the excellent mechanical and thermal stability. The dimethylaminoethyl methacrylate (DMAEMA) is grafted with brominated PPO by quaternization, where it contains cationic groups, i.e. quaternary ammonium, and photopolymerized groups, i.e. methacrylate C = C. This resulting prepolymer can be fast polymerized under UV irradiation via C = C from DMAEMA. This structure is synergistically regulated by the amounts of crosslinker DMAEMA and modifier N-bromosuccinimide. The optimized membrane exhibits an excellent ion exchange capacity of 2.19 mmol g−1, a water uptake of 38.17 %, and a tensile strength of 4.8 MPa. Meanwhile, its electrolyzer cell performance achieves a density of 580 mA cm−2 at an adjusted voltage of 2.1 V, and the desalination rate of seawater during electrodialysis reaches 98.34 %. This work provides a universal and facile fabrication route for high-performance AEMs.

Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High-Voltage Ultrahigh-Ni Cathode.

High-voltage ultrahigh-Ni cathodes (LiNixCoyMn1-x-yO2, x≥0.9) can significantly enhance the energy density and cost-effectiveness of Li-ion batteries beyond current levels. However, severe Li-Ni antisite defects and their undetermined dynamic evolutions during high-voltage cycling limit the further development of these ultrahigh-Ni cathodes. In this study, we quantify the dynamic evolutions of the Li-Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh-Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li-Ni antisite defects and controlled Ni migrations are essential for achieving stable high-voltage cycling structures in ultrahigh-Ni cathodes. This is further demonstrated by the optimized ultrahigh-Ni cathode, where reduced dynamic evolutions of the Li-Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.

Spontaneous Production of H2O2 at the Liquid-Ice Interface: A Potential Source of Atmospheric Oxidants.

We present experimental evidence for the spontaneous production of hydrogen peroxide (H2O2) at the liquid-ice interface during the freezing of dilute salt solutions. Specifically, sample solutions containing NaCl, NaBr, NH4Cl, and NaI at concentrations between 10-6 and 10-1 M were subjected to freezing-melting cycles and then analyzed for H2O2 content. The relationship between the production rate of H2O2 and the salt concentration follows that of the Workman-Reynolds freezing potential (WRFP) values as a function of the salt concentration. Our results suggest that H2O2 is formed at the liquid-ice interface from the self-recombination of hydroxyl radicals (OH·), produced from the oxidation of hydroxide anions due to the high electric field generated at the aqueous-ice interface under the WRFP effect. Furthermore, the involvement of O2 likely acting as an electron capturer could promote to produce more OH radicals and hydroperoxyl radicals (HO2·), thus enhancing the production of H2O2 at the liquid-ice interface. Overall, this study suggests a novel mechanism of H2O2 formation in ice via its spontaneous production at the liquid-ice interface, induced by the Workman-Reynolds effect.

Resistance artery vasodilator pathways involved in the antihypertensive effects of cocoa shell extract in rats exposed to fetal undernutrition.

Fetal undernutrition establishes the foundations for hypertension development, with oxidative stress being a key hallmark. A growing interest in nutraceuticals for treating hypertension and environmental waste concerns prompted the present study aiming to evaluate whether supplementation with a polyphenol enriched extract from cocoa shell (CSE), a by-product from the chocolate industry with antioxidant properties, reduces hypertension of developmental origin, thus improving mesenteric resistance artery (MRA) vasodilatation. Adult male and female offspring from rats exposed to 50% food restriction from mid-gestation (maternal undernutrition, MUN) and controls were used. Supplementation was given through a gelatine (vehicle, VEH) or containing CSE (250mgkg-1day-1) 5daysweek-1 for 3weeks. Systolic blood pressure (SBP) was assessed by tail-cuff plethysmography. MRA function was studied by wire myography, and superoxide anion and nitric oxide were investigated by fluorescent indicators and confocal microscopy. Compared to control-VEH, MUN-VEH males showed significantly higher SBP, reduced MRA as well as relaxation to ACh, sodium nitroprusside and the AMPK agonist 5-aminoimidazole-4-carboxamide riboside, but not to isoproterenol. In MUN males, endothelial endothelium-derived hyperpolarizing factor and nitric oxide were unaltered, but MRA released a vasoconstrictor prostanoid and produced higher levels of superoxide anion. CSE normalized blood pressure and improved all above-mentioned MRA alterations in MUN males without an effect on control counterparts, except the reduction of superoxide anion. MUN-VEH females were normotensive and only showed a tendency towards larger superoxide anion production, which was abolished by CSE. CSE supplementation reduces SBP improving endothelium-dependent and independent MRA vasodilatation, related to local superoxide anion reduction, being a potential nutraceutical ingredient to counteract hypertension, in addition to contributing to the circular economy. KEY POINTS: Fetal undernutrition induces hypertension in males associated with deficient resistance artery vasodilatation, being normalized by cocoa shell extract (CSE). Release of a cyclooxygenase-derived contractile factor is the main endothelial alteration, which is abolished by CSE. AMPK and soluble guanylyl cyclase-mediated relaxation are also reduced in smooth muscle cells from maternal undernutrition resistance arteries, being improved by CSE. Vascular oxidative damage caused by excess superoxide anion generation can account for impaired vasodilatation, which is improved by CSE. The capacity of CSE to improve relaxation is probably related to its antioxidant bioactive factors, and thus cocoa shell is a potential food by-product to treat hypertension.

An Approach to Estimate the Refractive Index and the Electronic Polarizability of the Ternary Ag2O-B2O3-TeO2 Glasses.

Each of the static properties such as refractive index (n0), cation ( ), and anion ( ) oxide polarizabilities for the ternary 30Ag2O⋅xB2O3⋅(70 - x)TeO2 (30AgBTe) glasses has been predicted theoretically from those of the binary 30Ag2O-70B2O3 and 30Ag2O-70TeO2 glasses. This can be done based on two assumptions: that each of these static properties (n0, , and ) can be considered as an additive property and that ternary 30AgBTe glasses can be treated as a mixture of two binary 30Ag2O-70B2O3 and 30Ag2O-70TeO2 glasses. In addition, n0 values for the ternary 30AgBTe glasses can be predicted in terms of and values for the ternary 30AgBTe glasses, and these later properties can be predicted from that of two binaries like as n0 at first stage. The n0 values obtained by using two methods are exactly the same for the corresponding compositions in the studied glasses, confirming the validity of the two assumptions and the procedure described in the present work. This conclusion is valid for the ternary glasses with a fixed content of either basic former/or modifier oxides for all compositions such as xPbO⋅(40 - x)Sb2O3⋅60B2O3 and 30Ag2O⋅xB2O3⋅(70 - x)TeO2 glasses, respectively.

Effect of the length of TiO2 nanotubes on the photoelectrochemical oxidation of phenylacetic acid anions

Effect of the length of TiO2 nanotubes on the photoelectrochemical oxidation of phenylacetic acid anions

Sulfate salt assistant fabrication of Fe-doped Ni2P modified with SO42−/carbon as highly efficient oxygen evolution reaction electrocatalyst

The incorporation of oxyanion groups offers a greater potential for enhancing the activity of oxygen evolution reaction (OER) electrocatalysts compared to traditional metal cations doping, owing to their unique configurations and high electronegativity. However, the incorporation of oxyanion groups that differ from those derived from the oxidation of anions in transition metal monoxides poses significant challenges, thereby limiting further applications of oxyanion group modification approach. Herein, we present a novel sulfate salt assistant approach to fabricate Fe-doped Ni2P modified with SO42−/carbon (Fe-Ni2P-S/C) nanofibers as highly efficient OER electrocatalyst. The optimized Fe-Ni2P-S/C nanofibers display superb OER activity, requiring low overpotentials of 266, 323, and 357 mV at 100, 500, and 1000 mA cm−2, respectively. Theoretical calculations reveal that the co-adsorption of PO43− and SO42− on the surface of reconstructed electrocatalyst can reduce the energy barrier of rate-determining step, thereby resulting in enhanced OER activity. The present study emphasizes the crucial role played by anion groups in OER activity as well as proposes a novel approach for incorporating anion groups into electrocatalysts.

Achieving High-Capacity Cathode Presodiation Agent Via Triggering Anionic Oxidation Activity in Sodium Oxide.

Compensating for the irreversible loss of limited active sodium (Na) is crucial for enhancing the energy density of practical sodium-ion batteries (SIBs) full-cell, especially when employing hard carbon anode with initially lower coulombic efficiency. Introducing sacrificial cathode presodiation agents, particularly those that own potential anionic oxidation activity with a high theoretical capacity, can provide additional sodium sources for compensating Na loss. Herein, Ni atoms are precisely implanted at the Na sites within Na2O framework, obtaining a (Na0.89Ni0.05□0.06)2O (Ni-Na2O) presodiation agent. The synergistic interaction between Na vacancies and Ni catalyst effectively tunes the band structure, forming moderate Ni-O covalent bonds, activating the oxidation activity of oxygen anion, reducing the decomposition overpotential to 2.8V (vs Na/Na+), and achieving a high presodiation capacity of 710 mAh/g≈Na2O (Na2O decomposition rate >80%). Incorporating currently-modified presodiation agent with Na3V2(PO4)3 and Na2/3Ni2/3Mn1/3O2 cathodes, the energy density of corresponding Na-ion full-cells presents an essential improvement of 23.9% and 19.3%, respectively. Further, not limited to Ni-Na2O, the structure-function relationship between the anionic oxidation mechanism and electrode-electrolyte interface fabrication is revealed as a paradigm for the development of sacrificial cathode presodiation agent.

First-principles calculations to investigate the impact of fluorine doping on electrochemical properties of Li-rich Li2MnO3 layered cathode materials.

Li-rich layered oxides are promising candidates for high-capacity Li-ion battery cathode materials. In this study, we employ first-principles calculations to investigate the effect of F doping on Li-rich Li2MnO3 layered cathode materials. Our findings reveal that both Li2MnO3 and Li2MnO2.75F0.25 exhibit significant volume changes (greater than 10%) during deep delithiation, which could hinder the cycling of more Li ions from these two materials. For Li2MnO3, it is observed that oxygen ions lose electrons to compensate for charge during the delithiation process, leading to a relatively high voltage plateau. After F doping, oxidation occurs in both the cationic (Mn) and anionic (O) components, resulting in a lower voltage plateau at the beginning of the charge, which can be attributed to the oxidation of Mn3+ to Mn4+. Additionally, F doping can somewhat suppress the release of oxygen in Li2MnO3, improving the stability of anionic oxidation. However, the increase of the activation barriers for Li diffusion can be observed after F doping, due to stronger electrostatic interactions between F- and Li+, which adversely affects the cycling kinetics of Li2MnO2.75F0.25. This study enhances our understanding of the impact of F doping in Li2MnO3 based on theoretical calculations.

Induced Anion Redox before Full Oxidation of Ru4+/Ru5+ through Local Configuration Modulation in P2-Na0.67[Mg0.33Ru0.67]O2

The study of anionic redox in layered-oxide cathodes for Na-ion batteries (NIBs) has been extensive, aiming to attain high-energy density. The involvement of Mn4+ or Ru5+ oxidation states is known to be crucial for the anionic O2 −/O− reaction during Na+ de/intercalation. Nevertheless, our findings indicate that anionic redox can activate in Ru-based layered-oxide cathodes prior to complete Ru4+/Ru5+ oxidation. By employing first-principles calculation and experimental techniques, we disclose that additional Na+ deintercalation from P2-Na0.33[Mg0.33Ru0.67]O2 relies on anionic oxidation after extracting 0.33 mol Na+ from P2-Na0.67[Mg0.33Ru0.67]O2, concomitant with cationic oxidation of Ru4+/Ru4.5+. Specifically, only the oxygen adjacent to 2Mg/1Ru is implicated in anionic redox during Na+ de/intercalation, indicating that the Na–O–Mg arrangement in the P2-Na0.33[Mg0.33Ru0.67]O2 structure significantly reduces the thermodynamic stability of anionic redox compared to cationic redox. Through O anionic and Ru cationic reactions, P2-Na0.67[Mg0.33Ru0.67]O2 demonstrates a substantial specific capacity of ∼172 mA h g− 1 and exceptional power capability, facilitated by facile Na+ diffusion and reversible structural changes during charge/discharge. These findings propose an innovative strategy to enhance anionic redox activity by modifying the local oxygen environment, paving the way for high-energy-density cathode materials in NIBs.

Accessing Cation and Anion Redox in a 1-D Iron-Chalcogenide, Na3Fe2S4-XSex (x = 0, 2, & 4), in Na-Ion Batteries

The utilization of anionic redox activity is gaining significant interest in chalcogen based alkali-ion batteries. In this study, we are reporting reversible Na-ion (de)intercalation in one-dimensional structure of Na3Fe2S4-xSex (x = 0, 2, and 4). The crystal structure of Na3Fe0.5 2+Fe0.5 3+Q4 (Q = S and Se) can be visualized as a mixed valent iron, Fe2+/Fe3+ , forming infinite edge-shared chain of FeQ 4 tetrahedra with Na-ion residing in the interchain voids. While cycling the cathodes within a potential range of 1.5 – 2.5 V vs. Na/Na+, we could reversibly (de)intercalate one mole of Na from the structure. Mössbauer spectroscopy reveals a complete Fe2+ to Fe3+ oxidation in all the charged samples. Substitution of less electronegative Se2– in the structure systematically lowers the Fe2+/3+ redox couple during cycling. After 100 cycles at 1C rate, the cathode retains 83 % of its initial reversible capacity. While cycling the same cathode at a higher voltage range of 1.5 – 3.0 V, we observed a flat plateau profile at ~2.6 V with capacity reaching 255 mAh/g for Na3Fe2S4 cathode. This high capacity can be directly attributed to the anion oxidation for the charge compensation process during ~3.0 Na-ion deintercalation as supported by XPS analysis. The flat plateau profile further decreases from 2.6 to 2.5 V with the substitution of Se2–. The GITT results show two distinct kinetic behavior for the cation (fast) and anion (sluggish) redox. The decoupling of cation and anion redox in this system can enable us to understand and optimize the utilization of both redox chemistries to achieve a high energy density cathode.

Enhanced Electrical Conductivity of Polyoxometalates by Bridging with Mixed‐Valent Multinuclear Platinum Complexes

AbstractPolyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (<10−10 Scm−1), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d0 metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs. Utilized with the electronic interactions between bridging oxygen atoms with the highest occupied molecular orbital in the POMs and the metal dz2 orbitals in the multinuclear platinum complexes, and three mixed‐valent assemblies were synthesized and characterized. Simply mixing Keggin‐type or Dawson‐type POMs with tetranuclear or trinuclear platinum complexes in solution afforded three single crystals, and all three compounds were paramagnetic with mixed oxidation states and better conductivities at room temperature than the parent compounds.

Enhanced Electrical Conductivity of Polyoxometalates by Bridging with Mixed-Valent Multinuclear Platinum Complexes.

Polyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (<10-10 Scm-1), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d0 metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs. Utilized with the electronic interactions between bridging oxygen atoms with the highest occupied molecular orbital in the POMs and the metal dz2 orbitals in the multinuclear platinum complexes, and three mixed-valent assemblies were synthesized and characterized. Simply mixing Keggin-type or Dawson-type POMs with tetranuclear or trinuclear platinum complexes in solution afforded three single crystals, and all three compounds were paramagnetic with mixed oxidation states and better conductivities at room temperature than the parent compounds.

Multiple Stabilization Effects of Benzylhydrazine on Scalable Perovskite Precursor Inks for Improved Perovskite Solar Cell Production

AbstractPerovskite precursor inks suffer various forms of degradation, such as iodide anion oxidation and organic cation breakdown, hindering reliable perovskite solar cell manufacturing. Here we report that benzylhydrazine hydrochloride (BHC) not only retards the buildup of iodine as previously reported but also prevents the breakdown of organic cations. Through investigating BHC and iodine chemical reactions, we elucidate protonation and dehydration mechanisms, converting BHC to harmless volatile compounds, thus preserving perovskite film crystallization and solar cell performance. This inhibition effect lasts nearly a month with minimal BHC, contrasting control inks without BHC where organic cations fully react in less than a week. This enhanced understanding, from additive stabilization to end products, promises improved perovskite solar cell production reliability.

Multiple Stabilization Effects of Benzylhydrazine on Scalable Perovskite Precursor Inks for Improved Perovskite Solar Cell Production.

Perovskite precursor inks suffer various forms of degradation, such as iodide anion oxidation and organic cation breakdown, hindering reliable perovskite solar cell manufacturing. Here we report that benzylhydrazine hydrochloride (BHC) not only retards the buildup of iodine as previously reported but also prevents the breakdown of organic cations. Through investigating BHC and iodine chemical reactions, we elucidate protonation and dehydration mechanisms, converting BHC to harmless volatile compounds, thus preserving perovskite film crystallization and solar cell performance. This inhibition effect lasts nearly a month with minimal BHC, contrasting control inks without BHC where organic cations fully react in less than a week. This enhanced understanding, from additive stabilization to end products, promises improved perovskite solar cell production reliability.

Cation Vacancies Enable Anion Redox in Li Cathodes.

Conventional Li-ion battery intercalation cathodes leverage charge compensation that is formally associated with redox on the transition metal. Employing the anions in the charge compensation mechanism, so-called anion redox, can yield higher capacities beyond the traditional limitations of intercalation chemistry. Here, we aim to understand the structural considerations that enable anion oxidation and focus on processes that result in structural changes, such as the formation of persulfide bonds. Using a Li-rich metal sulfide as a model system, we present both first-principles simulations and experimental data that show that cation vacancies are required for anion oxidation. First-principles simulations show that the oxidation of sulfide to persulfide only occurs when a neighboring vacancy is present. To experimentally probe the role of vacancies in anion redox processes, we introduce vacancies into the Li2TiS3 phase while maintaining a high valency of Ti. When the cation sublattice is fully occupied and no vacancies can be formed through transition metal oxidation, the material is electrochemically inert. Upon introduction of vacancies, the material can support high degrees of anion redox, even in the absence of transition metal oxidation. The model system offers fundamental insights to deepen our understanding of structure-property relationships that govern reversible anion redox in sulfides and demonstrates that cation vacancies are required for anion oxidation, in which persulfides are formed.

Structural evolution and electronic properties of anionic plutonium-doped oxygen clusters

Plutonium oxides are important in actinide chemistry and nuclear industry activities, and the demand and interest in enriching knowledge of plutonium chemistry is growing increasingly significant. However, unlike uranium oxide clusters, few studies related to the geometry and bonding properties of anionic plutonium oxide clusters have been reported. Here we explored the geometries, photoelectron spectra, and electronic properties of anionic plutonium oxide clusters by means of unbiased structural searches coupled with density-functional theory (DFT). The results show that the PuO6− cluster with a high D2h symmetry formed by a linear O-Pu-O plutonyl unit with two O2 units exhibits excellent stability. In addition, the HOMO–LUMO gap value of PuO6− cluster are 4.35 eV and 3.41 eV for the α- and β-orbitals, respectively, as well as the vertical detachment energy (VDE) of 4.20 eV. In the analysis of molecular orbitals and adaptive natural density partitioning in oxygen-rich systems, the σ bonds between plutonium atom and oxygen ligands, primarily from the Pu-5f and O-2p orbitals, are responsible for the goodish stability of PuO6− cluster. We hope that the current work can enrich the geometrical configuration of plutonium oxide oxygen clusters and provide reference information for the subsequent research work.