Surface Oxygen Research Articles

Revealing the degradation mechanism of calcium-based air electrodes in reversible solid oxide cells under chromium contaminants

Calcium-based perovskite La0.6Ca0.4Fe0.8Co0.2O3-δ (LCFC) with stable structure is the promising air electrode used in reversible solid oxide cells, and its application in cell stack must consider its Cr poisoning resistance ability. Herein, the Cr poisoning effect of it is studied in this work. The results indicate the strong reaction between LCFC and the Cr contaminations, forming undesirable CaCrO4 impurities, which significantly reduce the activity of ORR/OER. Both the decayed performance and reversible stability are also observed in SOFC and SOEC modes under the Cr contaminations, and the main reason comes from the reduced activity of the oxygen surface exchange processes and the blocked gas diffusion process by the impurities. A worse degenerated performance in SOFC mode than that in SOEC mode is also found in this work. Beyond that, the mechanism of the reaction between chromium contaminants and the Ca-segregation of the electrodes is discussed by the nucleation theory.

An active and stable PrOx-modified open-straight pore (La0.8Sr0.2)0.98MnO3-δ-Sc0.18Zr0.82O2-δ air electrode for reversible solid oxide cells

Air electrode supported reversible solid oxide cells (RSOCs) have drawn increasing attention for the capability of fuel flexibility and well bonding between the air electrode and electrolyte. However, the high concentration polarization and sluggish oxygen reduction/evolution reaction (ORR/OER) has significantly restricted the practical applications. Herein, finger-like (La0.8Sr0.2)0.98MnO3-δ-Sc0.18Zr0.82O2-δ (LSM98-SSZ) air electrode supported symmetrical and single cells are successfully fabricated by phase inversion tape-casting technology. The open-straight pores formed on the air electrode support can facilitate the gas transport and catalyst impregnation. The ORR/OER activity of LSM98-SSZ air electrode is largely increased with the introduction of impregnated PrOx nano catalyst, showing a low polarization resistance (Rp) of 0.06 Ω cm2 and great stability for 550 h at 700 oC. Furthermore, the LSM98-SSZ supported cell with PrOx modification shows a remarkable peak power density of 1.0 W cm-2 and electrolysis current density of 1.09 A cm-2 at 1.3 V at 750 oC. The enhanced performance is primarily ascribed to the facilitated oxygen surface exchange.

The Fate of the Formic Acid Proton on the Anatase TiO2(101) Surface

AbstractAs a prototype adsorption reaction of gas Brønsted acid on oxides, we study the adsorption of formic acid on anatase. We perform infrared spectroscopy measurements of adsorbed HCOOH and HCOOD on TiO2 nanopowders, from 13 K up to room temperature in an ultra‐high vacuum chamber. We assign the IR signals via computed spectra from nuclear quantum dynamics simulations using our divide‐and‐conquer semiclassical ab initio molecular dynamics method. The acid proton forms an extraordinarily short and strong hydrogen bond with the surface oxygen. The strength of this hydrogen bond, that compares to H bonds in ice at high pressures, is at the root of a substantial redshift with respect to the typical free OH stretching frequency, which eludes its straightforward detection.

Tuning CO2 Hydrogenation to Light Olefin Selectivity via Cu/Zn/Zr Supported on Modified SAPO‐34

AbstractTo alleviate CO2 emissions and reduce reliance on fossil fuels, a groundbreaking bifunctional catalyst system was introduced, which ingeniously merged CZZ with modified SAPO‐34 zeolite, to convert CO2 into light olefins. Different metals were impregnated into SAPO‐34 to form MeSAPO‐34 (Me = Zn, Zr, Mn) and the metal Zr content was altered. Furthermore, CZZ and MeSAPO‐34 was combined into CZZ/MeSAPO‐34 composite catalysts, which was used for CO2 hydrogenation. The MeSAPO‐34 and xZrSAPO‐34 catalysts were rigorously characterized by various techniques, revealing key physicochemical attributes. This innovative approach harnessed the synergistic effects between the metallic CZZ component and the modified zeolite to facilitate a series of reactions, effectively generating C2‐C4‐rich hydrocarbons. Benefiting from weak acid, higher oxygen vacancy concentration and interactions between components, the CZZ/ZrSAPO‐34 catalyst system has shown remarkable efficiency in enhancing the light olefin selectivity. The key aspects of this system are its ability to modulate surface acidity and oxygen vacancy concentration, thus creating favorable conditions for light olefin production via enhanced tandem reaction based on CO2 hydrogenation. This work enriches our insight into designing novel composite catalysts for promoting CO2 conversion and hence mitigating CO2 emissions.

Unveiling the influence of dopants on structural, defect chemistry, morphological and optical characteristics of NiO nanostructures

Abstract In this paper, undoped and doped (Fe, Co and Fe-Co) nickel oxide (NiO) nanostructures have been synthesized using co-precipitation method. Prepared samples were characterized for the structural, compositional, morphological and optical properties using x-ray diffraction, scanning electron microscopy (SEM), Energy dispersive spectrocopy (EDS), UV-visible spectroscopy and photoluminescence spectroscopy. Structural analysis confirmed the single cubic phase formation of undoped and doped samples. Defect chemistry showed that Fe-Co co-doped NiO possesses a lower density of defects than other samples. SEM results revealed the agglomeration of particles. EDS results confirmed the presence of Ni, O, Fe and Co in the respective undoped and doped samples. Optical analysis revealed the band edge shifts with the incorporation of dopants in the NiO crystal lattice confirmed the variation of band gap energy. Emission peaks were observed in the UV and visible regions. The Incorporation of dopants in the crystal lattice causes variation of emission centers. Surface oxygen vacancies and imperfections significantly impact the emission characteristics of NiO. Variable spectral response of NiO with dopant incorporation has potential for optoelectronic applications.

Ultra-efficient Ru and Nb Co-Modified CeO2 Catalysts for Catalytic Oxidation of 1,2-Dichloroethane.

The oxidation of chlorinated volatile organic compounds on CeO2 is hindered by its high susceptibility to chlorine poisoning, resulting in a reduced efficiency and stability. In this study, Ru- and Nb-co-modified CeO2 catalysts were designed to achieve excellent activity, stability, and CO2 selectivity in the catalytic oxidation of 1,2-dichloroethane (EDC). The formation of Nb-O-Ce bonds was observed to enhance the surface acidic sites, thereby improving HCl selectivity and reducing the production of chlorinated byproducts. Meanwhile, it inhibits the formation of Ru-O-Ce and promotes the generation of highly dispersed RuO2 particles on the surface, enhancing the redox properties and mobility of the surface oxygen, thus increasing CO2 selectivity. In situ diffuse reflectance infrared Fourier transform spectroscopy results revealed that chlorine species preferentially attach to Nb species rather than to oxygen vacancies on the Ru/Nb/CeO2 catalyst. This allows more alkane groups to oxidize to formate on the oxygen vacancies, reducing byproduct concentration. Additionally, the oxidation of alkane groups to carboxylic acids is initiated on the Nb species, completing a comprehensive oxidation process under the synergistic effect of RuO2.

Simultaneous Catalytic Oxidation of Benzene and Toluene over Pd-CeZrOx Catalysts

Since actual industrial emissions contain a wide range of volatile organic compounds, studies into the simultaneous catalytic degradation of multi-component VOCs are essential. This work developed Pd-CeZrOx samples for the simultaneous elimination of benzene and toluene. Firstly, CeZrOx supports were synthesized using several methods (co-precipitation, CTAB template co-precipitation, and sol–gel method). Pd active species were then added into the 1.0Pd-CeZrOx samples using the impregnation procedure. XRD, BET, NH3-TPD, Raman, EPR, XPS, and H2-TPR were utilized to analyze the as-prepared Pd-CeZrOx samples. The catalytic performance tests reveal that the performance of 1.0Pd-CeZrOx-CTAB outperforms that of 1.0Pd-CeZrOx-PM and 1.0Pd-CeZrOx-CASG, and 1.0Pd-CeZrOx-CTAB displays superior catalytic activity for both benzene and toluene oxidation. The improved redox properties, the abundant surface oxygen vacancies, and the surface Pd2+ species of the 1.0Pd-CeZrOx-CTAB sample may be responsible for the simultaneous degradation activity of benzene and toluene.

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO2, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Long-Term Selective Photoelectrochemical Glycerol Oxidation via Oxygen Vacancy Modulated Tungsten Oxide with Self-Healing.

The photoelectrochemical selective oxidation of biowaste glycerol into the high value-added material, along with hydrogen production, holds significant promise for advancing renewable and sustainable energy technologies. Here, the surface oxygen state of tungsten oxide is modified to selectively oxidize glycerol into glyceraldehyde, a high-value-added material, and the selectivity is maintained over a prolonged period using the photo-stimulated self-recovery capability. The surface-coordinated photoelectrode exhibits high charge transfer efficiency to glycerol and favorable glycerol adsorption capacity, enabling the selective conversion of glycerol. At 1.2 VRHE in a 2m glycerol electrolyte adjusted to pH 2, the tungsten oxide photoelectrode achieves a photocurrent density of 2.58mA cm-2 and a production rate of 378.8mmol m-2h-1 with selectivity of 86.1%. The high selectivity is preserved for 18 h by utilizing the self-healing capability of tungsten oxide to restore initial states modified by photoelectrochemical oxidation. This work sheds light on the design of highly efficient metal oxide photoelectrodes for selective biomass oxidation over extended periods.

Regulation of Surface Oxygen Vacancies on Ce-Based Catalysts for Dimethyl Carbonate Direct Synthesis from CO2 and CH3OH

Regulation of Surface Oxygen Vacancies on Ce-Based Catalysts for Dimethyl Carbonate Direct Synthesis from CO₂ and CH₃OH

Boosted 1,2-Dichloroethane Deep Destruction over CoRu/Al2O3 Bifunctional Catalysts via Surface Oxygen and Water Molecule Synergistic Activation.

Developing efficacious catalysts with superior Cl resistance and polychlorinated byproduct inhibition capability is crucial for realizing the environmentally friendly purification of chlorinated volatile organic compounds (CVOCs). Activating CVOC molecules and desorbing Cl species by modulating the metal-oxygen property is a promising strategy to fulfill these. Herein, a bifunctional CoRu/Al2O3 catalyst with synergistic Co and Ru interactions (Ru-O-Co species) was rationally fabricated, which possesses abundant surface Co2+ and Ruδ+ sites and collaboratively facilitates the activation of lattice oxygen (O2-) and molecular oxygen (O2 → O2- → O-), accelerating 1,2-dichloroethane (1,2-DCE) decomposition via the reaction route of enolic species → aldehydes → carboxylate/carbonate. Furthermore, CoRu/Al2O3 stimulates 1,2-DCE oxidation under humid conditions as H2O molecules can be easily activated to active *OH (potential oxidizing agent) over Ru species, accelerating C-Cl dissociation and Cl desorption and promoting the transformation of catecholate-type (C═O) species to easily oxidizable carboxylic acid (COOH) species, remarkably suppressing the formation of hazardous CCl4 and CHCl2CH2Cl. This study provides critical insights into the development of bifunctional catalysts to synergistically activate surface oxygen species and H2O molecules for industrial CVOC stable and efficient elimination.

Cation rearrangement at tetrahedral sites in the Cu/ZnAl2O4 spinel enhancing CO2 hydrogenation to methanol

Cu/ZnAl2O4 spinel is a promising catalyst for CO2-to-methanol due to its dual-site H2 activation. However, controlling surface properties and metal-support interactions (MSI) through the coordination environment of spinel cations remains underexplored. Herein, the occupancy of Zn2+ and Al3+ cations in Cu/ZnAl2O4 spinel is fine-tuned by manipulating the calcination atmosphere. More disordered structures (AlO4 and ZnO6) observed on the CZA-Ar catalyst benefit the creation of oxygen vacancies and surface hydroxyl groups, which facilitate the formation of highly dispersed small-sized Cu species. This enhances MSI and hydrogen spillover effects, thereby boosting CO2 conversion and the space-time yield (STY) of methanol. High-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the crucial formate intermediates form at tetrahedral sites in ZnAl2O4 spinel, with more Al-HCOO- species observed on the CZA-Ar catalyst due to the formation of AlO4. This work advances the understanding of spinel catalysts in CO2 hydrogenation to methanol.

Nanostructured defects-rich black-ZnO/biowaste-derived carbon composites for efficient visible light-driven hydrogen generation: A study on the role of C–Zn@C–O–Zn interface

The use of a highly efficient and noble-metal-free cocatalyst, which is being pursued to create hydrogen (H2) via photocatalysis, has been the subject of many studies. In this work, a unique ultrasonication-assisted laser beam irradiation process is employed to synthesize a new carbon material generated from pineapple peel biowaste (ppC) and mix it with oxygen-deficient black zinc oxide (b-ZnOvac) nanoparticles. In the ppCx@b-ZnOvac nanostructures, the XPS analysis verified the presence of surface oxygen (O2) defects and vacancies as well as chemical interactions between carbon and zinc via carbon-zinc (C–Zn) and carbon-oxygen-zinc (C–O–Zn) connection interfaces. Following optimization, the visible light active photocatalytic H2 production rate of the ppC10@b-ZnOvac nanostructures reached 215.92 μmol h−1 g−1, which was the highest. The positive synergistic interaction between b-ZnOvac and ppC is responsible for the significant increase in the rate of H2 generation. Furthermore, the significant chemical bond between ppC and b-ZnOvac via the C–Zn/C–O–Zn interface, as well as the development of surface O2 vacancy defects in b-ZnOvac, improve the efficient transfer of energetic electrons and make visible active photocatalytic H2 production from methanol in the ppCx@b-ZnOvac nanostructures easier. Our work presents a new strategy for chemically generating affordable carbon materials through the use of metal oxide-based photocatalysts with surface O2 vacancy defects and bio-waste. Applications such as water splitting, energy production, and environmental remediation show promise for these advanced materials for large-scale field applications.

Aerobic Oxidation of Vanillyl Alcohol to Vanillin Over CeO2‐Co3O4 Catalyst

AbstractA promising CeO2‐Co3O4 (9 : 1 mole ratio based on oxides) non‐noble metal based mixed oxide catalyst was explored for selective oxidation of vanillyl alcohol with molecular oxygen to produce vanillin under atmosphere pressure. In particular, to enhance its efficiency, this catalyst was prepared by adopting different preparation methods namely, template assisted, coprecipitation with and without surfactant, wet‐impregnation, and solution combustion. The prepared catalysts were characterized by XRD, Raman, BET surface area, ICP‐OES, FE‐SEM, HR‐TEM, H2‐TPR, and XPS. Among various catalysts investigated, the template assisted synthesized catalyst exhibited superior activity (100 % conversion and selectivity) and high stability. The better activity of this catalyst was found to be due to reduced crystallite size, high specific surface area (92 m2/g), more surface oxygen, and improved redox behaviour as confirmed from XRD, BET surface area, XPS, and H2‐TPR analysis, respectively. The stability of the catalyst was tested by reusability test and was observed that there is not much decrease in the catalytic activity up to five cycles. Further, the catalytic activity was optimized by varying the reaction parameters such as time, solvent, temperature, and catalyst weight.

ZnO@NiO core-shell heterojunction photoanode modified with NiOOH co-catalyst for high-performance self-powered photoelectrochemical-type UV photodetector

ZnO, a promising photoanode material, faces significant challenges in achieving high-efficient photoelectrochemical (PEC) type UV photodetectors due to inadequate charge separation and sluggish surface reaction kinetics. Constructing heterojunction nanostructures by coupling of p-NiO to n-ZnO nanowire arrays with well-aligned energy band positions presents a feasible strategy for enhancing PEC-type photodetector performance. Herein, we demonstrate that the designed ZnO@NiO core–shell nanowire arrays form a spatial charge transfer channel, facilitating efficient generation and extraction of charge carriers. The exceptional catalytic properties of NiOOH, derived from the transformation of NiO in an aqueous alkaline environment, serve as a potent co-catalyst, effectively accelerating the kinetics of the surface oxygen evolution reaction. Benefiting from the synergistic effect of the heterojunction and cocatalyst, the optimized photoanode achieves a high responsivity of 438.36 mA/W, a large detectivity of 4.85 × 1012 Jones, and rapid response time of 150.05/150.26 ms, while simultaneously exhibiting long-time PEC stability. This work highlights the critical role of nanostructure design in developing high-performance self-powered UV photodetectors.

Mechanisms of Cd immobilization in contaminated calcareous soils with different textural classes treated by acid- and base-modified biochars

Acid or base modification of biochars has shown promise for enhancing the immobilization of potentially toxic elements (PTEs) such as cadmium (Cd) in contaminated soils. However, limited information is available on the interaction between soil textural classes and modified biochar application for Cd stabilization in contaminated calcareous soils. Therefore, the objective of the study was to examine the extent of Cd immobilization in contaminated calcareous soils with diverse textural classes, utilizing both acid (HNO3) and alkali (NaOH) modified and unmodified biochars derived from sheep manure and rice husk residues. The modified or unmodified biochars were applied at a rate of 2% (w/w) to Cd-contaminated silty clay loam, loam, and sandy loam soils, followed by a 90-day incubation at field water capacity. Sequential extraction and EDTA-release kinetics studies were used to assess the effect of the treatments on the extent and mechanisms of Cd immobilization. Among the treatments, acid-modified manure biochar was most effective at reducing water soluble and exchangeable Cd fractions (-20.5%), by converting them into metal oxide and organic matter bound fractions. This effectiveness was primarily attributed to the significant increase in surface oxygen functional groups in the acid-modified biochar which could promote Cd complexation. However, the acid-modified manure biochar released more immobilized Cd during EDTA extraction than the base-modified manure biochar, suggesting that EDTA extraction of R-O-Cd complexes was easier than extracting Cd associated with insoluble compounds. This difference was likely due to the acidic pH and lower ash content of the acid-modified biochars compared to the base-modified manure biochars. Additionally, the extent of Cd immobilization was lower in sandy loam soil, highlighting the importance of immobilizing Cd in light-textured soils to prevent its transfer to organisms.

In‐Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water‐Gas Shift Reaction

AbstractIn situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water‐gas shift (RWGS) reaction. Surface oxygen atoms in various Mo‐based catalysts are removed in H2‐containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt‐dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal−1 ⋅ h−1 at 600 °C has been achieved over in situ carbonized H‐intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.

Morphology Regulation and Oxygen Vacancy Construction Synergistically Boosting the Piezocatalytic Degradation and Pure Water Splitting of SrTiO3.

In recent years, the development of high-efficiency piezoelectric materials is an effective means to make full use of the mechanical energy widely existing in the environment. However, there are few reports on multi-strategies synergistically improving piezocatalytic activity, and the mechanism of synergistic enhancement of piezocatalytic activity also receives less attention. Herein, the SrTiO3 nanorods decorated with tunable surface oxygen vacancy concentrations are prepared. Oxygen vacancy-optimized SrTiO3 nanorods exhibit efficient and undifferentiated piezocatalytic degradation activities for both anionic and cationic dyes under ultrasonic vibration. More importantly, it can split water into H2 and H2O2 with high production rates of 540 and 332 µmol g-1 h-1 without adding any sacrificial agents and cocatalysts, respectively. Mechanism analyses demonstrate that the 1D structure is beneficial to mechanical energy harvesting, and the surface oxygen vacancy induces larger surface asymmetry and piezoelectric response, synergically enhancing the piezocatalytic activity of SrTiO3 nanorods. In addition, metal deposition experiments under different conditions show that SrTiO3 nanorods possess abundant reactive catalytic sites in the piezocatalytic reaction process. This work provides a further understanding of piezocatalysis in piezoelectric nanomaterials and is important for the development of efficient piezoelectric catalysts.

Tailoring glassy carbon electrode surface with FeBiO3 for electrochemical detection of dinitrophenol isomers

ABSTRACT This study presents a simultaneous, rapid, and highly sensitive electrochemical detection of 2,4- and 2,5-dinitrophenol isomers using an iron bismuth oxide (FeBiO3)-modified glassy carbon electrode (GCE). The FeBiO3-modified GCE exhibited superior electrochemical performance over bare GCE, Bi2O3-modified GCE, and Fe2O3-modified GCE, as demonstrated by electrochemical impedance spectroscopy (EIS) with the potassium ferricyanide (Fe(CN6)3-/4-) standard. The synthesised electrocatalyst FeBiO3 exhibited strong absorption both in the visible and UV regions of the spectrum, attributed to band gap transitions and charge transfer transitions linked to its Bi2O3 and Fe2O3 components. The morphology and the structure of the FeBiO3 were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), while Fourier transform infrared spectroscopy (FTIR) was employed to analyse the functional groups attached to the surface of FeBiO3. Cyclic voltammetry (CV) clearly demonstrated an increased current and improved peak resolution for the reduction of 2,4- and 2,5-dinitrophenols at the FeBiO3/GCE, compared to the bare GCE. The mechanism shows that the reduction of 2,4- and 2,5-dinitrophenols occurs through interactions with the surface oxygen functional groups of FeBiO3, resulting in the stepwise reduction of their NO2 groups to hydroxyamino compounds and then to nitrosophenols. Using square wave voltammetry (SWV), the reduction peak currents were significantly improved, enhancing detection sensitivity beyond that reported in previous works. A linear range from 1 µM to 1 mm for the dinitrophenol isomers was established, with detection limits of 0.07 µM for 2,4-dinitrophenol and 0.09 µM for 2,5-dinitrophenol. The FeBiO3/GCE electrode showed interferences with mono-nitrophenols and mono-/di-chlorophenols in solution but maintained excellent long-term stability and reproducibility, allowing it to effectively detect dinitrophenol isomers in drinking water, tap water, and wastewater samples.

Double-Shell Co3O4 with Rich Surface Octahedron Oxygen Vacancies for High-Selectivity Electrocatalytic Chlorine Evolution.

The development of non-noble-metal-based chlorine evolution reaction (CER) catalysts with excellent activity, kinetics, and selectivity is urgently needed but still remains a major challenge. In this study, a morphology self-evolving and surface octahedron oxygen-vacancy-generating strategy is applied at double-shell nanospheres to obtain the target hierarchical double-shell Co3O4 nanospheres with abundant surface oxygen vacancies (DS-Co3O4-OVs). The DS-Co3O4-OVs display an overpotential of only 52 mV to reach a current density of 10 mA cm-2 in which an excellent chlorine selectivity of 98.9-99.9% is attained, which is better than that of the commercial RuO2/IrO2. Furthermore, density functional theory calculations demonstrate that the involved oxygen vacancies can not only limit the lattice oxygen mechanism of the oxygen evolution reaction process but also significantly improve the kinetics of the Volmer step to enhance the CER performance. Meanwhile, the unique hierarchical double-shell nanospheres can enhance the mass feeding and promote the rate-determining step of the Krishtalik step chlorine gas desorption reaction for enhanced kinetics. The self-evolution of non-noble catalysts with surface octahedron vacancies and the related exploration of the CER mechanism may provide a novel design idea for CER catalysts.