Spin Symmetry Breaking-induced Hubbard Gap Near-Closure in N-coordinated MnO2 for Enhanced Aqueous Zinc-Ion Battery Performance.

Transition metal oxides (TMOs) are promising cathode materials for aqueous zinc ion batteries (ZIBs), however, their performance is hindered by a substantial Hubbard gap, which limits electron transfer and battery cyclability. Addressing this, we introduce a heteroatom coordination approach, using triethanolamine to induce axial N coordination on Mn centers in MnO2, yielding N-coordinated MnO2 (TEAMO). This approach leverages the change of electronegativity disparity between Mn and ligands (O and N) to disrupt spin symmetry and augment spin polarization. This enhancement leads to the closure of the Hubbard gap, primarily driven by the intensified occupancy of the Mn eg orbitals. The resultant TEAMO exhibit a significant increase in storage capacity, reaching 351 mAh g-1 at 0.1 A g-1. Our findings suggest a viable strategy for optimizing the electronic structure of TMO cathodes, enhancing the potential of ZIBs in energy storage technology.

Electronegative Phosphorus-Integrated Co2+ Active Sites for Enhanced Electrocatalytic Nitrogen Reduction.

In the quest for proficient electrocatalysts for ammonia's electrocatalytic nitrogen reduction, cobalt oxides, endowed with a rich d-electron reservoir, have emerged as frontrunners. Despite the previously evidenced prowess of CoO in this realm, its ammonia yield witnesses a pronounced decline as the reaction unfolds, a phenomenon linked to the electron attrition from its Co2+ active sites during electrocatalytic nitrogen reduction reaction (ENRR). To counteract this vulnerability, we harnessed electron-laden phosphorus (P) elements as dopants, aiming to recalibrate the electronic equilibrium of the pivotal Co active site, thereby bolstering both its catalytic performance and stability. Our empirical endeavors showcased the doped P-CoO's superior credentials: it delivered an impressive ammonia yield of 49.6 and, notably, a Faradaic efficiency (FE) of 9.6% at -0.2 V versus RHE, markedly eclipsing its undoped counterpart. Probing deeper, a suite of ex-situ techniques, complemented by rigorous theoretical evaluations, was deployed. This dual-pronged analysis unequivocally revealed CoO's propensity for an electron-driven valence metamorphosis to Co3+ post-ENRR. In stark contrast, P-CoO, fortified by P doping, exhibits a discernibly augmented ammonia yield. Crucially, P's intrinsic ability to staunch electron leakage from the active locus during ENRR ensures the preservation of the valence state, culminating in enhanced catalytic dynamism and fortitude. This investigation not only illuminates the intricacies of active site electronic modulation in ENRR but also charts a navigational beacon for further enhancements in this domain.

Unlocking Spin Gates of Transition Metal Oxides via Strain Stimuli to Augment Potassium Ion Storage.

Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost-effectiveness and a broad potential window. However, their full potential is limited by poor understanding of their slow reaction kinetics and stability issues. This study diverges from conventional complex nano-structuring, concentrating instead on spin-related charge transfer and orbital interactions to enhance the reaction dynamics and stability of TMOs during energy storage processes. We successfully reconfigured the orbital degeneracy and spin-dependent electronic occupancy by disrupting the symmetry of magnetic cobalt (Co) sites through straightforward strain stimuli. The key to this approach lies in the unfilled Co 3d shell, which serves as a spin-dependent regulator for carrier transfer and orbital interactions within the reaction. We observed that the opening of these 'spin gates' occurs during a transition from a symmetric low-spin state to an asymmetric high-spin state, resulting in enhanced reaction kinetics and maintained structural stability. Specifically, the spin-rearranged Al-Co3O4 exhibited a specific capacitance of 1371 F g-1, which is 38 % higher than that of unaltered Co3O4. These results not only shed light on the spin effects in magnetic TMOs but also establish a new paradigm for designing electrochemical energy storage materials with improved efficiency.

Zn Single-Atom Catalysts Enable the Catalytic Transfer Hydrogenation of α,ß-Unsaturated Aldehydes.

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,ß-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

Beneficial Effects of Echinacoside on Cognitive Impairment and Diabetes in Type 2 Diabetic db/db Mice.

INTRODUCTION: Cognitive dysfunction is an important comorbidity of diabetes. Insulin resistance may play a critical role in diabetes-related cognitive impairment. Echinacoside (ECH), a natural phenylethanoid glycoside, is the active component of anti-diabetes prescriptions in traditional Chinese medicine. Its effect on modulating insulin resistance has been confirmed but modulating neurodegenerative disease remains unclear. METHODS: Db/db mice, a spontaneous type 2 diabetes mode, were intragastrically administered ECH by 300 mg/kg or an equivalent volume of saline. Weight, blood glucose, and insulin resistance index were measured. Morris water maze test was performed to observe the compound effects on cognition. Hippocampal lesions were observed by histochemical analysis. RESULTS: In db/db mice, ECH alleviated diabetes symptoms, memory loss, and hippocampal neuronal damage. Next, the expression of CD44 and phosphorylated tau was upregulated in diabetic mice. In addition, the insulin receptor substrate-1/phosphatidylinositol 3-kinase /protein kinase B signaling pathway was dysregulated in diabetic mice. All these dysregulations could be reversed by ECH. DISCUSSION: This study provides theoretical support and experimental evidence for the future application of ECH in diabetic cognition dysfunction treatment, promoting the development of traditional medicines.

Dual-role transcription factors stabilize intermediate expression levels.

Precise control of gene expression levels is essential for normal cell functions, yet how they are defined and tightly maintained, particularly at intermediate levels, remains elusive. Here, using a series of newly developed sequencing, imaging, and functional assays, we uncover a class of transcription factors with dual roles as activators and repressors, referred to as condensate-forming level-regulating dual-action transcription factors (TFs). They reduce high expression but increase low expression to achieve stable intermediate levels. Dual-action TFs directly exert activating and repressing functions via condensate-forming domains that compartmentalize core transcriptional unit selectively. Clinically relevant mutations in these domains, which are linked to a range of developmental disorders, impair condensate selectivity and dual-action TF activity. These results collectively address a fundamental question in expression regulation and demonstrate the potential of level-regulating dual-action TFs as powerful effectors for engineering controlled expression levels.

Modulating the d-Band Center of Palladium via Ethylene Glycol Modification: Accelerating Had Desorption for Enhanced Formate Electrooxidation.

This study addresses the critical challenge in alkaline direct formate fuel cells (DFFCs) of slow formate oxidation reaction (FOR) kinetics as a result of strong hydrogen intermediate (Had) adsorption on Pd catalysts. We developed WO3-supported Pd nanoparticles (EG-Pd/WO3) via an organic reduction method using ethylene glycol (EG), aiming to modulate the d-band center of Pd and alter Had adsorption dynamics. Cyclic voltammetry demonstrated significantly improved Had desorption kinetics in EG-Pd/WO3 catalysts. Density functional theory (DFT) calculations revealed that the presence of EG reduces the d-band center of Pd, leading to weaker Pd-H bonds and enhanced Had desorption during the FOR. This research provides a new approach to optimize catalyst efficiency in DFFCs, highlighting the potential for more effective and sustainable energy solutions through advanced material engineering.

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OHad-Driven Had Removal.

Direct formate fuel cells have gained traction due to their eco-friendly credentials and inherent safety. However, their potential is hampered by the kinetic challenges of the formate oxidation reaction (FOR) on Pd-based catalysts, chiefly due to the unfavorable adsorption of hydrogen species (Had). These species clog the active sites, hindering efficient catalysis. Here, we introduce a straightforward strategy to remedy this bottleneck by incorporating Pd with Cu to expedite the removal of Pd-Had in alkaline media. Notably, Cu plays a pivotal role in bolstering the concentration of hydroxyl adsorbates (OHad) on the surface of catalyst. These OHad species can react with Had, effectively unblocking the active sites for FOR. The as-synthesized catalyst of PdCu/C exhibits a superior FOR performance, boasting a remarkable mass activity of 3.62 A mg-1. Through CO-stripping voltammetry, we discern that the presence of Cu in Pd markedly speeds up the formation of adsorbed hydroxyl species (OHad) at diminished potentials. This, in turn, aids the oxidative removal of Pd-Had, leveraging a synergistic mechanism during FOR. Density functional theory computations further reveal intensified interactions between adsorbed oxygen species and intermediates, underscoring that the Cu-Pd interface exhibits greater oxyphilicity compared to pristine Pd. In this study, we present both experimental and theoretical corroborations, unequivocally highlighting that the integrated copper species markedly amplify the generation of OHad, ensuring efficient removal of Had. This work paves the way, shedding light on the strategic design of high-performing FOR catalysts.

Activation of MnO6 Units via an Interfacial Electric Field: Electron Injection into Mn t2g for Rapid and Stable Sodium Ion Storage in CeO2 /MnOx.

Manganese-based oxides (MnOx ) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO2 /MnOx is constructed to obtain high electronic/ionic conductivity and structural stability of MnOx . The as-designed CeO2 /MnOx exhibits a remarkable capacity of 397 F g-1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t2g orbitals driven by the formed IEF. Correspondingly, the MnO6 units in MnOx are effectively activated, endowing the CeO2 /MnOx with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO2 /MnOx , which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnOx during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials.

Energizing Co Active Sites via d-Band Center Engineering in CeO2 -Co3 O4 Heterostructures: Interfacial Charge Transfer Enabling Efficient Nitrate Electrosynthesis.

The electrochemical nitrogen oxidation reaction (NOR) holds significant potential to revolutionize the traditional nitrate synthesis processes. However, the progression in NOR has been notably stymied due to the sluggish kinetics of initial N2 adsorption and activation processes. Herein, the research embarks on the development of a CeO2 -Co3 O4 heterostructure, strategically engineered to facilitate the electron transfer from CeO2 to Co3 O4 . This orchestrated transfer operates to amplify the d-band center of the Co active sites, thereby enhancing N2 adsorption and activation dynamics by strengthening the Co─N bond and diminishing the resilience of the N≡N bond. The synthesized CeO2 -Co3 O4 manifests promising prospects, showcasing a significant HNO3 yield of 37.96 µg h-1 mgcat -1 and an elevated Faradaic efficiency (FE) of 29.30% in a 0.1 m Na2 SO4 solution at 1.81 V versus RHE. Further substantiating these findings, an array of in situ methodologies coupled with DFT calculations vividly illustrate the augmented adsorption and activation of N2 on the surface of CeO2 -Co3 O4 heterostructure, resulting in a substantial reduction in the energy barrier pertinent to the rate-determining step within the NOR pathway. This research carves a promising pathway to amplify N2 adsorption throughout the electrochemical NOR operations and delineates a blueprint for crafting highly efficient NOR electrocatalysts.

Cortical somatostatin long-range projection neurons and interneurons exhibit divergent developmental trajectories.

The mammalian cerebral cortex contains an extraordinary diversity of cell types that emerge by implementing different developmental programs. Delineating when and how cellular diversification occurs is particularly challenging for cortical inhibitory neurons because they represent a small proportion of all cortical cells and have a protracted development. Here, we combine single-cell RNA sequencing and spatial transcriptomics to characterize the emergence of neuronal diversity among somatostatin-expressing (SST+) cells in mice. We found that SST+ inhibitory neurons segregate during embryonic stages into long-range projection (LRP) neurons and two types of interneurons, Martinotti cells and non-Martinotti cells, following distinct developmental trajectories. Two main subtypes of LRP neurons and several subtypes of interneurons are readily distinguishable in the embryo, although interneuron diversity is likely refined during early postnatal life. Our results suggest that the timing for cellular diversification is unique for different subtypes of SST+ neurons and particularly divergent for LRP neurons and interneurons.

Study design and rationale of COMPETE: Comparison of the effect of medication therapy in alleviating migraine with patent foramen ovale.

BACKGROUND: Previous studies have examined the impact of antithrombotic agents on Patent Foramen Ovale (PFO) in relation to migraine. However, differences in effectiveness of different antithrombotic agents and traditional migraine medications are not known. METHODS/DESIGN: This study is an investigator-initiated, randomized, multicenter, single-masked (outcomes assessor), and active-controlled parallel-group trial (ClinicalTrials.gov Identifier: NCT05546320), with the objective of evaluating the prevention efficacy of antithrombotic agents compared to first-line migraine medication in PFO patients. The trial involves 1,000 migraine patients with a right-to-left shunt at the atrial level, randomized in a 1:1:1:1 fashion to receive either aspirin 300 mg QD, clopidogrel 75 mg QD, rivaroxaban 20 mg QD, or the active-control metoprolol 25 mg BID. The primary efficacy end point is the response rate, defined as a 50% or greater reduction in the average migraine attack days per month or in the average number of migraine attacks per month at 12-week visit compared to baseline. CONCLUSIONS: The COMPETE trial aims to provide valuable insights into the comparative effectiveness of antithrombotic agents and standard migraine therapies in patients with PFO. This study holds the promise of advancing treatment approaches for individuals having migraines associated with PFO, thus addressing an important gap in current migraine management strategies.

High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation.

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO2), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO2 presents an impressive capacitance of 317 F g-1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t2g orbital. Additionally, the charge redistribution from Ni to the t2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.

DFT study of SF6 adsorption by Pd-doped hydroxyl-terminal modified Ti3C2Tx MXene.

CONTEXT: SF6 gas has a strong greenhouse effect, and how to treat SF6 in an environmentally friendly way has been a hot topic of current research. In this paper, the adsorption behavior of SF6 on the surface of Pd-doped hydroxyl-terminated modified Ti3C2Tx (i.e., Ti3C2(OH)2) was investigated based on the density functional theory using two-dimensional MXene as the catalyst. The structures of different Pd-doped Ti3C2(OH)2 were analyzed and the most structurally stable doped structures were selected as the basis for subsequent calculations. A large number of adsorption configurations were constructed and geometrically optimized, and the adsorption energy, charge transfer, differential charge density, and density of states of the systems were calculated in order to analyze the gas-solid interactions and find the surface active sites; compared with the adsorption performance of undoped Ti3C2(OH)2 on SF6, it was found that Pd doping played a less inhibitory role in the adsorption of SF6 on the Ti3C2(OH)2 surface. The results of this study can provide theoretical support for the use of Pd-doped Ti3C2(OH)2 as a catalyst for the degradation of SF6. METHODS: In this paper, simulations of SF6 adsorption on Ti3C2Tx surfaces are based on density functional theory and are carried out in the Dmol3 module of Material Studio. To better describe the non-uniform electron density of the actual system, the PBE functional in the generalized gradient approximation (GGA) was chosen for the optimization of the structure of the gas-solid interface system and the calculation of the relevant electronic properties, combined with the Grimme dispersion correction in the DFT-D dispersion correction for the electron exchange correlation term. Because both Pd and Ti are transition metal elements, the mode-conserving pseudopotential DNP basis set containing relativistic effects was chosen for the electronic wave function expansion. In this paper, an all-electron model is used for the inner core treatment of gas molecules and a density generalized semi-nuclear pseudopotential DSSP is used for the solid surface treatment.

Built-in Electric Field-Induced Work Function Reduction in C-Co3O4 for Efficient Electrochemical Nitrogen Reduction.

Co3O4 is a highly selective catalyst for the electrochemical conversion of N2 to NH3. However, the large work function (WF) of Co3O4 leads to unsatisfactory activity. To address this issue, a strong built-in electric field (BIEF) was constructed in Co3O4 by doping C atoms (C-Co3O4) to reduce the WF for improving the electrocatalytic performance. C-Co3O4 exhibited a remarkable NH3 yield of 38.5 µg h-1 mgcat-1 and a promoted FE of 15.1% at -0.3 V vs RHE, which were 2.2 and 1.9 times higher than those of pure Co3O4, respectively. Kelvin probe force microscopy (KPFM), zeta potential, and ultraviolet photoelectron spectrometry (UPS) confirmed the formation of strong BIEF and WF reduction in C-Co3O4. Additionally, in situ Raman measurements and density functional theory (DFT) calculations revealed the relationship between BIEF and WF and provided insights into the reaction mechanism. Our work offers valuable guidance for the design and development of more efficient nitrogen reduction catalysts.

Proteomic profiling of purified avian leukosis virus subgroup J particles.

While the presence of host cell proteins in virions and their role in viral life cycles have been demonstrated in various viruses, such characteristics have remained largely unknown in avian leukosis virus (ALV). To investigate whether this is the case in ALV, we purified high-integrity and high-purity virions from the avian leukosis virus subgroup J (ALV-J) and subjected them to proteome analysis using nano LC-MS/MS. This analysis identified 53 cellular proteins that are incorporated into mature ALV-J virions, and we verified the reliability of the packaged cellular proteins through subtilisin digestion and immunoblot analysis. Functional annotation revealed the potential functions of these proteins in the viral life cycle and tumorigenesis. Overall, our findings have important implications for understanding the interaction between ALV-J and its host, and provide new insights into the cellular requirements that define ALV-J infection.

Boosting CO2 Electroreduction to C2H4 via Unconventional Hybridization: High-Order Ce4+ 4f and O 2p Interaction in Ce-Cu2O for Stabilizing Cu.

Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu2O-based catalysts for the CO2 reduction reaction (CO2RR), owing to their capabilities in enhancing C-C coupling. However, the electrochemical instability of Cu+ in Cu2O leads to its inevitable reduction to Cu0, resulting in poor selectivity for C2+ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu+ through the construction of a Ce4+ 4f-O 2p-Cu+ 3d network structure in Ce-Cu2O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near Ef based on the high-order Ce4+ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu+ in Ce-Cu2O, compared with traditional d-p hybridization. Compared to pure Cu2O, the Ce-Cu2O catalyst increased the ratio of C2H4/CO by 1.69-fold during the CO2RR at -1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO2RR conditions with time resolution, identifying the well-maintained Cu+ species in the Ce-Cu2O catalyst. This work not only presents an avenue to CO2RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.

Modulating the Interfacial Water Network of Dual-Site Pd/FeOx/C Catalyst for Efficient Formate Electrooxidation.

The rational design of electrocatalysts for formate oxidation reaction (FOR) in alkaline media is crucial to promote the practical applications of direct formate fuel cells (DFFCs). The FOR kinetic on palladium (Pd) based electrocatalysts is strongly hindered by unfavorably adsorbed hydrogen (Had) as the major intermediate species blocking the active sites. Herein, we report a strategy of modulating the interfacial water network of dual-site Pd/FeOx/C catalyst to significantly enhance the desorption kinetics of Had during FOR. Aberration-corrected electron microscopy and synchrotron characterizations revealed the successful construction of Pd/FeOx interfaces on carbon support as a dual-site electrocatalyst for FOR. Electrochemical tests and in situ Raman spectroscopy results showed that Had could be effectively removed from the active sites of the as-designed Pd/FeOx/C catalyst. CO-stripping voltammetry and density functional theory calculations (DFT) demonstrated that the introduced FeOx could effectively accelerate the dissociative adsorption of water molecules on active sites, which accordingly generates adsorbed hydroxyl species (OHad) to facilitate the removal of Had during FOR. This work provides a novel route to develop advanced FOR catalysts for fuel cell applications.

Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d-Band Center in WS2 -WO3 for Enhanced Intermediate Adsorption.

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate-determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2 -WO3 to elevate the d-band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2 -WO3 exhibited a high NH3 yield of 62.38 µg h-1 mgcat -1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2 -WO3 upshifted the d-band center of W towards the Fermi level, leading to enhanced adsorption of -NH2 and -NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d-band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process.

Internal Electric Field Induced by Superexchange Interaction on Mn4+ -O2- -Ni2+ Unit Enables Highly Efficient Hybrid Capacitive Deionization.

Internal electric field (IEF) construction is an innovative strategy to regulate the electronic structure of electrode materials to promote charge transfer processes. Despite the wide use of IEF in various applications, the underlying mechanism of its formation in an asymmetric TM-O-TM unit still remains poorly understood. Herein, the essential principles for the IEF construction at electron occupancy state level and explore its effect on hybrid capacitive deionization (HCDI) performance is systematically investigated. By triggering a charge separation in Ni-MnO2 via superexchange interactions in a coordination structure unit of Mn4+ -O2- -Ni2+ , the formation of an IEF that can enhance charge transfer during the HCDI process is demonstrated. Experimental and theoretical results confirm the electrons transfer from O 2p orbital to TM (Ni2+ and Mn4+ ) eg orbital via superexchange interactions in the basic Mn4+ -O2- -Ni2+ coordination unit. As a result of the charge redistribution, the IEF endows Ni-MnO2 with superior electron and ion transfer property. This work presents a unique material design strategy that activates the electrochemical performance, and provides insights into the formation mechanism of IEF in an asymmetric TM-O-TM unit, which has potential applications in the construction of other innovative materials.