Cyanogel-Induced Facile Synthesis of Palladium Hydride for Electrocatalytic Oxygen Reduction.

Palladium hydride (PdHx) is one of the well-known electrocatalytic materials, yet its synthesis is still a challenge through an energy-efficient and straightforward method. Herein, we propose a new and facile cyanogel-assisted synthesis strategy for the preparation of PdH0.649 at a mild environment with NaBH4 as the hydrogen source. Unlike traditional inorganic Pd precursors, the unique Pd-CN-Pd bridge in Pdx[Pd(CN)4]y·aH2O cyanogel offers more favourable spatial sites for insertion of H atoms. The characteristic three-dimensional backbone of cyanogel also acts as a support scaffold resulting in the interconnected network structure of PdH0.649. Due to the incorporation of H atoms and interconnected network structure, the PdH0.649 achieves a high half-wave potential of 0.932 V, a high onset potential of 1.062 V, and a low activation energy, as well as a long-term lifetime for oxygen reduction reaction. Theoretical calculation demonstrates a downshift of the d-band centre of Pd in PdH0.649 owing to the dominant Pd-H incorporation that weakens the binding energies of the *OH intermediate species. Zn-air batteries (ZAB) based on PdH0.649 exhibits high power density, competitive open circuit voltage, and good stability, exceeding that of commercial Pt black.

Perspective on High-Stability Single-Crystal Li-Rich Cathode Materials for Li-Ion Batteries.

Benefiting from anionic and cationic redox reactions, Li-rich materials have been regarded as next-generation cathodes to overcome the bottleneck of energy density. However, they always suffer from cracking of polycrystalline (PC) secondary particles and lattice oxygen release, resulting in severe structural deterioration and capacity decay upon cycling. Single-crystal (SC) design has been proven as an effective strategy to relieve these issues in traditional Li-rich cathodes with PC morphology. Herein, we first reviewed the main synthesis routes of SC Li-rich materials including solid-state reaction, molten salt-assisted, and hydrothermal/solvothermal methods, in which the differences in grain morphology, electrochemical behaviors, and other properties induced by various routes were analyzed and discussed. Furthermore, the distinct characteristics were compared between SC and PC cathodes from the aspects of irreversible capacity, structural stability, capacity/voltage degradation, and gas release. Besides, recent advances in layered SC Li-rich oxide cathodes were summarized in detail, where the unique structural designs and modification strategies could greatly promote their structural/electrochemical stability. At last, challenges and perspectives for the emerging SC Li-rich cathodes were proposed, which provided an exceptional opportunity to achieve high-energy-density and high-stability Li-ion/metal batteries.

Use of spectroscopic process analytical technology for rapid quality evaluation during preparation of CHO cell culture media.

Media preparation parameters contribute significantly to media quality, cell culture performance, productivity, and product quality. Establishing proper media preparation procedures is critical for ensuring a robust CHO cell culture process. Process analytical technology (PAT) enables unique ways to quantify assessments and improve media quality. Here, cell culture media were prepared under a wide range of temperatures (40-80°C) and pH (7.6-10.0). Media quality profiles were compared using three real-time PATs: Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and excitation-emission matrix (EEM) spectroscopy. FTIR and Raman spectroscopies identified shifts in media quality under high preparation temperature (80°C) and at differing preparation pH which negatively impacted monoclonal antibody (mAb) production. In fed-batch processes for production of three different mAbs, viable cell density (VCD) and cell viability were mostly unaffected under all media preparation temperatures, while titer and cell specific productivity of mAb decreased when cultured in basal and feed media prepared at 80°C. High feed preparation pH alone was tolerated but cell growth and productivity profiles deviated from the control condition. Further, charge variants (main, acidic, basic species) and glycosylation (G0F, afucosylation, and high mannose) were examined. Statistically significant differences were observed for one or more of these quality attributes with any shifts in media preparation. In this study, we demonstrated strong associations between media preparation conditions and cell growth, productivity, and product quality. The rapid evaluation of media by PAT implementation enabled more comprehensive understanding of different parameters on media quality and consequential effects on CHO cell culture.

Single-embryo transcriptomic atlas of oxygen response reveals the critical role of HIF-1α in prompting embryonic zygotic genome activation.

Adaptive response to physiological oxygen levels (physO2; 5% O2) enables embryonic survival in a low-oxygen developmental environment. However, the mechanism underlying the role of physO2 in supporting preimplantation development, remains elusive. Here, we systematically studied oxygen responses of hallmark events in preimplantation development. Focusing on impeded transcriptional upregulation under atmospheric oxygen levels (atmosO2; 20% O2) during the 2-cell stage, we functionally identified a novel role of HIF-1α in promoting major zygotic genome activation by serving as an oxygen-sensitive transcription factor. Moreover, during blastocyst formation, atmosO2 impeded H3K4me3 and H3K27me3 deposition by deregulating histone-lysine methyltransferases, thus impairing X-chromosome inactivation in blastocysts. In addition, we found atmosO2 impedes metabolic shift to glycolysis before blastocyst formation, thus resulting a low-level histone lactylation deposition. Notably, we also reported an increased sex-dimorphic oxygen response of embryos upon preimplantation development. Together, focusing on genetic and epigenetic events that are essential for embryonic survival and development, the present study advances current knowledge of embryonic adaptive responses to physO2, and provides novel insight into mechanism underlying irreversibly impaired developmental potential due to a short-term atmosO2 exposure.

Low-loaded Ru on hollow SnO2 for enhanced electrocatalytic hydrogen evolution.

In response to the challenges of intermediate poisoning and the high cost of noble metal catalysts in the hydrogen evolution reaction (HER), we develop a Ru-doped SnO2 catalyst. This Ru-SnO2 catalyst has the characteristics of low Ru loading and a hollow structure, which endow it with good electrocatalytic activity and stability for the HER.

Role of amorphous engineering and cerium doping in NiFe oxyhydroxide for electrocatalytic water oxidation.

Amorphous engineering and atomistic doping provide an effective way to improve the catalytic activity in the oxygen evolution reaction (OER) of transition metal layered double hydroxides. Herein, Cerium (Ce) was introduced into NiFe-based oxyhydroxide using a modified aqueous sol-gel procedure. Ce as an electron acceptor promoted the coupling oxidation of Ni2+/3+ in NiFe oxyhydroxide, and the activated oxyhydroxide showed excellent catalytic activity in OER. The amorphous NiFeCe oxyhydroxide electrocatalyst demonstrated great modified OER catalytic activity under alkaline conditions and excellent cyclic stability, with an overpotential of only 284 mV at 50 mA cm-2, which was significantly better than amorphous NiFe oxyhydroxide and crystalline NiFeCe oxyhydroxide. Theoretical investigations further indicated that the overpotential of the rate-determining step (*OOH deprotonation) decreased from 0.66 to 0.41 V after Ce doping and strong electron interaction, effectively reducing the dependence of proton activity in the solution of OER, and optimizing the adsorption/desorption process of related oxygen-containing species in the reaction. This work also provides a good reference for optimizing OER activity by using rare-earth-metal induced electronic regulation strategies.

Fed-batch performance profiles for mAb production using different intensified N - 1 seed strategies are CHO cell-line dependent.

Recent optimizations of cell culture processes have focused on the final seed scale-up step (N - 1 stage) used to inoculate the production bioreactor (N-stage bioreactor) to enable higher inoculation cell densities (2-20 × 106 cells/mL), which could shorten the production culture duration and/or increase the volumetric productivity. N - 1 seed process intensification can be achieved by either non-perfusion (enriched-batch or fed-batch) or perfusion culture to reach those higher final N - 1 viable cell densities (VCD). In this study, we evaluated how different N - 1 intensification strategies, specifically enriched-batch (EB) N - 1 versus perfusion N - 1, affect cell growth profiles and monoclonal antibody (mAb) productivity in the final N-stage production bioreactor operated in fed-batch mode. Three representative Chinese Hamster Ovary (CHO) cell lines producing different mAbs were cultured using either EB or perfusion N - 1 seeds and found that the N-stage cell growth and mAb productivities were comparable between EB N - 1 and perfusion N - 1 conditions for two of the cell lines but were very different for the third. In addition, within the two similar cell growth cell lines, differences in cell-specific productivity were observed. This suggests that the impact of the N - 1 intensification process on production was cell-line dependent. This study revealed that the N - 1 intensification strategy and the state of seeds from the different N - 1 conditions may affect the outcome of the N production stage, and thus, the choice of N - 1 intensification strategy could be a new target for future upstream optimization of mAb production.

Effect of intubation in lateral position on placement of a double-lumen tube in patients undergoing unilateral video-assisted thoracic surgery: a randomied clinical trial.

Background: Approximately one-third of patients who undergo double-lumen tube (DLT) intubation in the conventional supine position experience DLT malposition. No randomized study investigates the effect of DLT intubation in the lateral position. We therefore aimed to evaluate the effect of intubation in lateral position on placement of a DLT compared to supine intubation, and to test primary hypothesis that lateral DLT intubation could reduce the incidence of DLT malposition. Methods: We randomly allocated 108 patients undergoing video-assisted thoracic surgery to receive DLT intubation in the comfortable and surgically required lateral position (lateral group) or in the supine position (supine group) from October to December 2022. The primary outcome was the incidence of DLT malposition defined as movement >1.0 cm to correct the DLT position. The secondary outcomes included intubation time, the frequency and duration of fibreoptic bronchoscopy, the need for re-intubation, intra-operative vital signs, and post-operative recovery. This trial is registered with the Chinese Clinical Trial Registry (ChiCTR2200060794). Findings: The incidence of DLT malposition was significantly lower in the lateral group (1/53 [2%]) than that in the supine group (16/53 [30%]; RR [95% confidence interval] of 0.06 [0.01-0.46]; P < 0.001). Lateral DLT intubation decreased the intubation time, the frequency and duration of fibreoptic bronchoscopy. The incidence of hypotension, post-operative sore throat, and upper-arm discomfort was lower in the lateral group. Other secondary outcomes were similar between groups. Interpretation: Lateral DLT intubation reduced the incidence of DLT malposition for patients undergoing video-assisted thoracic surgery. These results support that lateral DLT intubation offers more benefits and may be a superior option compared to conventional supine intubation. Funding: National Natural Science Foundation of China and of Zhejiang Province.

Recent advances in upstream process development for production of recombinant adeno-associated virus.

Recombinant adeno-associated virus (rAAV) is rapidly emerging as the preferred delivery vehicle for gene therapies, with promising advantages in safety and efficacy. Key challenges in systemic in-vivo rAAV gene therapy applications are the gap in production capabilities versus potential market demand and complex production process. This review summarizes current available information on rAAV upstream manufacturing processes and proposed optimizations for production. The advancements in rAAV production media were reviewed with proposals to speed up the cell culture process development. Furthermore, major methods for genetic element delivery to host cells were summarized with their advantages, limitations, and future directions for optimization. In addition, culture vessel selection criteria were listed based on production cell system, scale, and development stage. Process control at the production step was also outlined with an in-depth understanding of production kinetics and quality control.

Single-Atom Heterogeneous Catalysts: Human- and AI-Driven Platform for Augmented Designs, Analytics and Reality-Enabled Manufacturing.

Heterogeneous catalysts with targeted functionality can be designed with atomic precision, but it is challenging to retain the structure and performance upon the scaled-up manufacturing. Particularly challenging is to ensure the "atomic economy", where every catalytic site is most gainfully utilized. Given the emerging synergistic integration of human- and artificial intelligence (AI)-driven augmented designs (AD), augmented analytics (AA), and augmented reality manufacturing (AM) platforms, this minireview focuses on single-atom heterogeneous catalysts (SAHCs) and examines the current status, challenges, and future perspectives of translating atomic-level structural precision and data-driven discovery to next-generation industrial manufacturing. We critically examine the atomistic insights into structure-driven SAHCs functionality and discuss the opportunities and challenges on the way towards the synergistic human-AI collaborative data-driven platform capable of monitoring, analyzing, manufacturing, and retaining the atomic-scale structure and functions. Enhanced by the atomic-level AD, AA, and AM, evolving from the current high-throughput capabilities and digital materials manufacturing acceleration, this synergistic human-AI platform is promising to enable atom-efficient and atomically precise heterogeneous catalyst production.

Importing Antibonding-Orbital Occupancy through Pd-O-Gd Bridge Promotes Electrocatalytic Oxygen Reduction.

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 O3 , Eu2 O3 , and CeO2 ) by using RE metal-organic frameworks to tune the ORR performance of the Pd sites through the Pd-REx Oy interface interaction. Taking Pd-Gd2 O3 /C as a representative, it is identified that the strong coupling between Pd and Gd2 O3 induces the formation of the Pd-O-Gd bridge, which triggers charge redistribution of Pd and Gd2 O3 . The screened Pd-Gd2 O3 /C exhibits impressive ORR performance with high onset potential (0.986 VRHE ), half-wave potential (0.877 VRHE ), and excellent stability. Similar ORR results are also found for Pd-Sm2 O3 /C, Pd-Eu2 O3 /C, and Pd-CeO2 /C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2 O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR. The pH-dependent microkinetic modeling shows that Pd-Gd2 O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd-Gd2 O3 /C exhibits superior performance in Zn-air battery as an air cathode, implying its excellent practicability.

Establishment of a Murine Pulp Exposure Model with a Novel Mouth-Gag for Pulpitis Research.

Pulpitis, a common cause of natural tooth loss, leads to necrosis and loss of bioactivity in the inflamed dental pulp. Unraveling the mechanisms underlying pulpitis and its efficient treatment is an ongoing focus of endodontic research. Therefore, understanding the inflammatory process within the dental pulp is vital for improving pulp preservation. Compared to other in vitro experiments, a murine pulpitis model offers a more authentic and genetically diverse context to observe the pathological progression of pulpitis. However, using mice, despite their cost-effectiveness and accessibility, poses difficulties due to their small size, poor coordination, and low tolerance, complicating intraoral and dental procedures. This protocol introduces a novel design and application of a mouth-gag to expose mouse pulp, facilitating more efficient intraoral procedures. The mouth-gag, comprised of a dental arch readily available to most dentists and can significantly expedite surgical preparation, even for first-time procedures. Micro-CT, hematoxylin-eosin (HE) staining, and immunofluorescence staining were used to identify changes in morphology and cell expression. The aim of this article is to help researchers establish a more reproducible and less demanding procedure for creating a pulp inflammation model using this novel mouth-gag.

"Meiosis arrester" C-natriuretic peptide directly stimulates oocyte mtDNA accumulation and is implicated in aging-associated oocyte mtDNA loss.

C-natriuretic peptide (CNP) is the central regulator of oocyte meiosis progression, thus coordinating synchronization of oocyte nuclear-cytoplasmic maturation. However, whether CNP can independently regulate cytoplasmic maturation has been long overlooked. Mitochondrial DNA (mtDNA) accumulation is the hallmark event of cytoplasmic maturation, but the mechanism underlying oocyte mtDNA replication remains largely elusive. Herein, we report that CNP can directly stimulate oocyte mtDNA replication at GV stage, and deficiency of follicular CNP may contribute largely to lower mtDNA copy number in in vitro matured oocytes. The mechanistic study showed that cAMP-PKA-CREB1 signaling cascade underlies the regulatory role of CNP in stimulating mtDNA replication and upregulating related genes. Of interest, we also report that CNP-NPR2 signaling is inhibited in aging follicles, and this inhibition is implicated in lower mtDNA copy number in oocytes from aging females. Together, our study provides the first direct functional link between follicular CNP and oocyte mtDNA replication, and identifies its involvement in aging-associated mtDNA loss in oocytes. These findings, not only update the current knowledge of the functions of CNP in coordinating oocyte maturation but also present a promising strategy for improving in vitro fertilization outcomes of aging females.

Hierarchical PdNi alloy nanochains coupled with Ni(OH)2 nanosheets to enhance CO-poisoning resistance for the methanol oxidation reaction.

Hybridizing Pd-based electrocatalysts with Ni-based species has been recognized as an effective pathway to enhance the catalytic performance for the methanol oxidation reaction (MOR). However, doping Ni-based species with heterogeneous valences into Pd nanocrystals still remains challenging, although heterogeneous valence Ni species may result in improved properties of Pd from different aspects. Herein, a facile one-pot synthetic method is reported to simultaneously introduce alloyed Ni0 into Pd lattices and couple hydroxy Ni2+ species with a Pd surface, generating 1D porous PdNi alloy nanochains@Ni(OH)2 nanosheet hybrids (PdNi NCs@Ni(OH)2 NSs). Borane-tert-butylamine (C4H14BN) plays the key role in realizing the formation of Ni-based species with heterogeneous valence. On one hand, it works as a reducing agent to facilitate the doping of alloyed Ni0 into the lattice of Pd nanochains. On the other hand, it raises the solution pH value and converts the remaining [Ni(CN)4]2- into Ni(OH)2 nanosheets. Each component of the PdNi NCs@Ni(OH)2 NSs plays an important role: Pd serves as the active site, alloyed Ni0 modifies the electronic structure of Pd, and Ni(OH)2 provides abundant OHads species to strengthen the anti-poisoning capability, thus greatly enhancing the activity, CO-tolerance, and durability for the MOR.

A Versatile Extended Stöber Approach to Monodisperse Sub-40 nm Carbon Nanospheres for Stabilizing Atomically Dispersed Fe─N4 Sites Toward Efficient Oxygen Reduction Electrocatalysis.

The development of atomically dispersed iron-nitrogen-carbon (Fe─N─C) catalysts as an alternative to precious platinum holds great potential for the substantial progress of a variety of oxygen reduction reaction (ORR)-associated energy conversion technologies. Nevertheless, the precise synthesis of Fe─N─C single atomic catalysts (SACs) with a high density of accessible active sites and pronounced electrocatalytic performance still remains an enormous challenge. Herein, an innovative extended Stöber method is designed for the controllable preparation of monodisperse small-sized N-doped carbon colloidal nanospheres (≈40 nm) anchoring atomically isolated Fe─N4 sites (abbreviated as Fe-SA@N-CNSs hereafter) with a narrow size distribution and high uniformity. Benefiting from the single Fe─N4 moieties and the unique spherical carbon substrate, the resultant Fe-SA@N-CNSs exhibit excellent ORR activity, outstanding long-term durability, and methanol tolerance in KOH electrolyte. More impressively, when further assembled into a flexible solid-state rechargeable zinc-air battery (ZAB), the Fe-SA@N-CNSs-driven ZAB delivers a higher open circuit voltage, a larger power density, and robust cycling/mechanical stability, outperforming the state-of-the-art Pt/C-based counterpart and further testifying the great potential of the as-prepared Fe-SA@N-CNSs in diverse ORR-related practical energy devices. The developed extended Stöber method provides an efficient and versatile avenue toward the preparation of a series of well-defined SACs for diverse electrocatalytic systems.

Rare-Earth-Modified Metal-Organic Frameworks and Derivatives for Photo/Electrocatalysis.

Metal-organic frameworks (MOFs) and their derivatives have attracted much attention in the field of photo/electrocatalysis owing to their ultrahigh porosity, tunable properties, and superior coordination ability. Regulating the valence electronic structure and coordination environment of MOFs is an effective way to enhance their intrinsic catalytic performance. Rare earth (RE) elements with 4f orbital occupancy provide an opportunity to evoke electron rearrangement, accelerate charged carrier transport, and synergize the surface adsorption of catalysts. Therefore, the integration of RE with MOFs makes it possible to optimize their electronic structure and coordination environment, resulting in enhanced catalytic performance. In this review, progress in current research on the use of RE-modified MOFs and their derivatives for photo/electrocatalysis is summarized and discussed. First, the theoretical advantages of RE in MOF modification are introduced, with a focus on the roles of 4f orbital occupancy and RE ion organic coordination ligands. Then, the application of RE-modified MOFs and their derivatives in photo/electrocatalysis is systematically discussed. Finally, research challenges, future opportunities, and prospects for RE-MOFs are also discussed.

Assessing the efficacy of bleaching powder in disinfecting marine water: Insights from the rapid recovery of microbiomes.

Single-bleaching powder disinfection is a highly prevalent practice to disinfect source water for marine aquaculture to prevent diseases. However, due to the decay of active chlorine and the presence of disinfectant resistance bacteria (DRB), the effects of bleaching powder on prokaryotic community compositions (PCCs) and function in marine water remain unknown. In the present study, the source water in a canvas pond was treated with the normal dose of bleaching powder, and the impact on PCCs and functional profiles was investigated using 16S rRNA gene amplicon sequencing. The bleaching powder strongly altered the PCCs within 0.5 h, but they began to recover at 16 h, eventually achieving 76% similarity with the initial time at 72 h. This extremely rapid recovery was primarily driven by the decay of Bacillus and the regrowth of Pseudoalteromonas, both of which are DRB. Abundant community not only help PCCs recover but also provide larger functional redundancy than rare community. During the recovery of PCCs, stochastic processes drove the community assembly. After 72 h, five out of seven identified disinfectant resistance genes related to efflux pump systems were highly enriched, primarily in Staphylococcus and Bacillus. However, 15 out of the 16 identified antibiotic resistance genes (ARGs) remained unchanged compared to the initial time, indicating that bleaching powder does not contribute to ARGs removal. Overall, the findings demonstrate that single-bleaching powder disinfection cannot successfully meet the objective of disease prevention in marine aquaculture water due to the extremely rapid recovery of PCCs. Hence, secondary disinfection or novel disinfection strategies should be explored for source water disinfection.

The Biological Roles of Puccinia striiformis f. sp. tritici Effectors during Infection of Wheat.

Puccinia striiformis f. sp. tritici (Pst) is the causative agent of wheat stripe rust, which can lead to a significant loss in annual wheat yields. Therefore, there is an urgent need for a deeper comprehension of the basic mechanisms underlying Pst infection. Effectors are known as the agents that plant pathogens deliver into host tissues to promote infection, typically by interfering with plant physiology and biochemistry. Insights into effector activity can significantly aid the development of future strategies to generate disease-resistant crops. However, the functional analysis of Pst effectors is still in its infancy, which hinders our understanding of the molecular mechanisms of the interaction between Pst and wheat. In this review, we summarize the potential roles of validated and proposed Pst effectors during wheat infection, including proteinaceous effectors, non-coding RNAs (sRNA effectors), and secondary metabolites (SMs effectors). Further, we suggest specific countermeasures against Pst pathogenesis and future research directions, which may promote our understanding of Pst effector functions during wheat immunity attempts.

Template-assisted Fabrication of O-doped CoP Microflowers with Optimal Electronic Modulation for Electrochemical Hydrogen Evolution.

Exploring efficient, affordable and stable electrocatalyst toward hydrogen evolution reaction (HER) is of great scientific significance for the practical implementation of the water splitting. The heteroatom doping represents a serviceable strategy to further elevate the catalytic performance for a transition metal-based electrocatalyst because of the electronic regulation effect. Herein, a reliable self-sacrificial template-engaged approach is proposed to synthesize O-doped CoP (denoted as O-CoP) microflowers, which simultaneously considers the regualtion of electronic configuration via anion doping and sufficient exposure of active sites via nanostructure engineering. The suitable O incorporation content in CoP matrix could tremendously modify the electronic configuration, accelerate the charge transfer, promote the exposure of active sites, strengthen the electrical conductivity, and adjust the adsorption state of H*. Consequently, the optimized O-CoP microflowers with optimal O concentration display a remarkable HER property with a small overpotential of 125 mV to afford a current density of 10 mA cm-2 , a low Tafel slope of 68 mV dec-1 and long-term durability for 32 h under alkaline electrolyte, manifesting a considerable potential application for hydrogen production at large scale. The integration of anion incorporation and architecture engineering in this work will bring in a depth insight for the design of low-cost and effective electrocatalysts in energy conversion and storage systems.

Reinforcing CoO Covalency via Ce(4f)─O(2p)─Co(3d) Gradient Orbital Coupling for High-Efficiency Oxygen Evolution.

Rare-earth (RE)-based transition metal oxides (TMO) are emerging as a frontier toward the oxygen evolution reaction (OER), yet the knowledge regarding their electrocatalytic mechanism and active sites is very limited. In this work, atomically dispersed Ce on CoO is successfully designed and synthesized by an effective plasma (P)-assisted strategy as a model (P-Ce SAs@CoO) to investigate the origin of OER performance in RE-TMO systems. The P-Ce SAs@CoO exhibits favorable performance with an overpotential of only 261 mV at 10 mA cm-2 and robust electrochemical stability, superior to individual CoO. X-ray absorption spectroscopy and in situ electrochemical Raman spectroscopy reveal that the Ce-induced electron redistribution inhibits CoO bond breakage in the CoOCe unit site. Theoretical analysis demonstrates that the gradient orbital coupling reinforces the CoO covalency of the Ce(4f)─O(2p)─Co(3d) unit active site with an optimized Co-3d-eg occupancy, which can balance the adsorption strength of intermediates and in turn reach the apex of the theoretical OER maximum, in excellent agreement with experimental observations. It is believed that the establishment of this Ce-CoO model can set a basis for the mechanistic understanding and structural design of high-performance RE-TMO catalysts.