Boron-Induced Interstitial Effects Drive Water Oxidation on Ordered Ir-B Compounds.

Interstitial filling of light atoms strongly affects the electronic structure and adsorption properties of the parent catalyst due to ligand and ensemble effects. Different from the conventional doping and surface modification, constructing ordered intermetallic structures is more promising to overcome the dissolution and reconstruction of active sites through strong interactions generated by atomic periodic arrangement, achieving joint improvement in catalytic activity and stability. However, for tightly arranged metal lattices, such as iridium (Ir), obtaining ordered filling atoms and further unveiling their interstitial effects are still limited by highly activated processes. Herein, we report a high-temperature molten salt assisted strategy to form the intermetallic Ir-B compounds (IrB1.1) with ordered filling by light boron (B) atoms. The B residing in the interstitial lattice of Ir constitutes favorable adsorption surfaces through a donor-acceptor architecture, which has an optimal free energy uphill in rate-determining step (RDS) of oxygen evolution reaction (OER), resulting in enhanced activity. Meanwhile, the strong coupling of Ir-B structural units suppresses the demetallation and reconstruction behavior of Ir, ensuring catalytic stability. Such B-induced interstitial effects endow IrB1.1 with higher OER performance than commercial IrO2, which is further validated in proton exchange membrane water electrolyzers (PEMWEs).

Sharply expanding single-atomically dispersed Fe-N active sites through bidirectional coordination for oxygen reduction.

For Fe-NC systems, high-density Fe-N sites are the basis for high-efficiency oxygen reduction reaction (ORR), and P doping can further lower the reaction energy barrier, especially in the form of metal-P bonding. However, limited to the irregular agglomeration of metal atoms at high temperatures, Fe-P bonds and high-density Fe-N cannot be guaranteed simultaneously. Here, to escape the random and violent agglomeration of Fe species during high-temperature carbonization, triphenylphosphine and 2-methylimidazole with a strong metal coordination capability are introduced together to confine Fe growth. With the aid of such bidirectional coordination, the high-density Fe-N site with Fe-P bonds is realized by in situ phosphorylation of Fe in an Fe-NC system (Fe-P-NC) at high temperatures. Impressively, the content of single-atomically dispersed Fe sites for Fe-P-NC dramatically increases from 2.8% to 65.3% compared with that of pure Fe-NC, greatly improving the ORR activity in acidic and alkaline electrolytes. The theoretical calculation results show that the generated Fe2P can simultaneously facilitate the adsorption of intermediates to Fe-N4 sites and the electron transfer, thereby reducing the reaction energy barrier and obtaining superior ORR activity.

Bicontinuous RuO2 nanoreactors for acidic water oxidation.

Improving activity and stability of Ruthenium (Ru)-based catalysts in acidic environments is eager to replace more expensive Iridium (Ir)-based materials as practical anode catalyst for proton-exchange membrane water electrolyzers (PEMWEs). Here, a bicontinuous nanoreactor composed of multiscale defective RuO2 nanomonomers (MD-RuO2-BN) is conceived and confirmed by three-dimensional tomograph reconstruction technology. The unique bicontinuous nanoreactor structure provides abundant active sites and rapid mass transfer capability through a cavity confinement effect. Besides, existing vacancies and grain boundaries endow MD-RuO2-BN with generous low-coordination Ru atoms and weakened Ru-O interaction, inhibiting the oxidation of lattice oxygen and dissolution of high-valence Ru. Consequently, in acidic media, the electron- and micro-structure synchronously optimized MD-RuO2-BN achieves hyper water oxidation activity (196 mV @ 10 mA cm-2) and an ultralow degradation rate of 1.2 mV h-1. A homemade PEMWE using MD-RuO2-BN as anode also conveys high water splitting performance (1.64 V @ 1 A cm-2). Theoretical calculations and in-situ Raman spectra further unveil the electronic structure of MD-RuO2-BN and the mechanism of water oxidation processes, rationalizing the enhanced performance by the synergistic effect of multiscale defects and protected active Ru sites.

Hybrid supercapacitors using metal-organic framework derived nickel-sulfur compounds.

HYPOTHESIS: Metal-organic frameworks (MOFs) are highly suitable precursors for supercapacitor electrode materials owing to their high porosity and stable backbone structures that offer several advantages for redox reactions and rapid ion transport. EXPERIMENTS: In this study, a carbon-coated Ni9S8 composite (Ni9S8@C-5) was prepared via sulfuration at 500 ℃ using a spherical Ni-MOF as the sacrificial template. FINDING: The stable carbon skeleton derived from Ni-MOF and positive structure-activity relationship due to the multinuclear Ni9S8 components resulted in a specific capacity of 278.06 mAh·g-1 at 1 A·g-1. Additionally, the hybrid supercapacitor (HSC) constructed using Ni9S8@C-5 as the positive electrode and the laboratory-prepared coal pitch-based activated carbon (CTP-AC) as the negative electrode achieved an energy density of 69.32 Wh·kg-1 at a power density of 800.06 W·kg-1, and capacity retention of 83.06 % after 5000 cycles of charging and discharging at 5 A·g-1. The Ni-MOF sacrificial template method proposed in this study effectively addresses the challenges associated with structural collapse and agglomeration of Ni9S8 during electrochemical reactions, thus improving its electrochemical performance. Hence, a simple preparation method is demonstrated, with broad application prospects in supercapacitor electrodes.

Constructing Symmetry-Mismatched RuxFe3-xO4 Heterointerface-Supported Ru Clusters for Efficient Hydrogen Evolution and Oxidation Reactions.

Ru-related catalysts have shown excellent performance for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR); however, a deep understanding of Ru-active sites on a nanoscale heterogeneous support for hydrogen catalysis is still lacking. Herein, a click chemistry strategy is proposed to design Ru cluster-decorated nanometer RuxFe3-xO4 heterointerfaces (Ru/RuxFe3-xO4) as highly effective bifunctional hydrogen catalysts. It is found that introducing Ru into nanometric Fe3O4 species breaks the symmetry configuration and optimizes the active site in Ru/RuxFe3-xO4 for HER and HOR. As expected, the catalyst displays prominent alkaline HER and HOR performance with mass activity much higher than that of commercial Pt/C as well as robust stability during catalysis because of the strong interaction between the Ru cluster and the RuxFe3-xO4 support, and the optimized adsorption intermediate (Had and OHad). This work sheds light on a promsing approach to improving the electrocatalysis performance of catalysts by the breaking of atomic dimension symmetry.

Symmetry-Broken Ru Nanoparticles with Parasitic Ru-Co Dual-Single Atoms Overcome the Volmer Step of Alkaline Hydrogen Oxidation.

Efficient dual-single-atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual-single-atom site generation remains formidable challenges. Here, we break the local symmetry of ultra-small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1 Ru1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen-affine Co atom disrupts the symmetry of ultra-small Ru nanoparticles, resulting in parasitic Ru and Co dual-single-atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2 O. As anticipated, Co1 Ru1,n /rGO exhibits ultrahigh mass activity (7.68 A mgRu -1 ) at 50 mV and exchange current density (0.68 mA cm-2 ), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi-single-atom and metal nanoparticle catalysis.

Correlating Single-Atomic Ruthenium Interdistance with Long-Range Interaction Boosts Hydrogen Evolution Reaction Kinetics.

Correlated single-atom catalysts (c-SACs) with tailored intersite metal-metal interactions are superior to conventional catalysts with isolated metal sites. However, precise quantification of the single-atomic interdistance (SAD) in c-SACs is not yet achieved, which is essential for a crucial understanding and remarkable improvement of the correlated metal-site-governed catalytic reaction kinetics. Here, three Ru c-SACs are fabricated with precise SAD using a planar organometallic molecular design and π-π molecule-carbon nanotube confinement. This strategy results in graded SAD from 2.4 to 9.3 Å in the Ru c-SACs, wherein tailoring the Ru SAD into 7.0 Å generates an exceptionally high turnover frequency of 17.92 H2 s-1 and a remarkable mass activity of 100.4 A mg-1 under 50 and 100 mV overpotentials, respectively, which is superior to all the Ru-based catalysts reported previously. Furthermore, density functional theory calculations confirm that Ru SAD has a negative correlation with its d-band center owing to the long-range interactions induced by distinct local atomic geometries, resulting in an appropriate electrostatic potential and the highest catalytic activity on c-SACs with 7.0 Å Ru SAD. The present study promises an attractive methodology for experimentally quantifying the metal SAD to provide valuable insights into the catalytic mechanism of c-SACs.

Ru Cluster Incorporated NiMoO(P)4 Nanosheet Arrays as High-Efficient Bifunctional Catalyst for Wind/Solar-To-Hydrogen Generation Systems.

Developing cost-efficient bifunctional water splitting catalysts is crucial for sustainable hydrogen energy applications. Herein, ruthenium (Ru)-incorporated and phosphorus (P)-doped nickel molybdate (Ru-NiMoO(P)4 ) nanosheet array catalysts are synthesized. Due to the synergy of Ru clusters and NiMoO(P)4 by the modulated electronic structure and the rich active sites, impressively, Ru-NiMoO(P)4 exhibits superior OER (194 mV @ 50 mA cm-2 ) and HER (24 mV @ 10 mA cm-2 ) activity in alkaline media, far exceeding that of commercial Pt/C and RuO2 catalysts. Meanwhile, as bifunctional catalyst, to drive the overall water splitting at the current density of 10 mA cm-2 , Ru-NiMoO(P)4 requires only 1.45 V and maintaining stable output for 100 h. Furthermore, Ru-NiMoO(P)4 also possesses excellent capability for seawater electrolysis hydrogen production. Moreover, the successful demonstration of wind and solar hydrogen production systems provide the feasibility of the ultra-low Ru loading catalyst for large-scale hydrogen production in the future.

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis.

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.

Ge-Regulated Ordered Phase in Pseudosphere-Structured LiNi0.5Mn1.5O4 Spinel Effectively Inhibits Mn Dissolution.

Due to the higher energy density, high thermal stability, and low cost, LiNi0.5Mn1.5O4 (LNMO) spinel, with a large voltage operating window, has been one of the most promising cathode materials for lithium-ion batteries (LIBs). However, the interfacial reaction between the cathode and electrolyte and the two-phase reaction within the bulk of LNMO would destroy the original structure and lead to capacity deterioration, posing a significant challenge. Therefore, the way to suppress the transition-metal (TM) dissolution in LNMO has attracted much attention. However, the ordered/disordered phase regulation by metal atom doping to prohibit TM dissolution has not been extensively explored. Herein, a Ge-doping strategy is proposed to adjust the ratio of disordered/ordered phases in LNMO, resulting in exceptional structural stability. For the modified spinel cathode, there is almost no voltage drop and the capacity retention is up to 92.2% over 1000 cycles at 1C. These results demonstrate that incorporating Ge into LNMO forms a robust structure that effectively increases the amount of Mn4+ while blocking the diffusion of TM ions. In addition, Ge-doping also protects the bulk from further reactions with electrolytes, significantly enhancing the interfacial stability and relieving voltage decay in cycling. This approach can also be applied to design other high-stability cathodes through ordered/disordered phase regulation.

Monomicelle-Directed Engineering of Strained Carbon Nanoribbons as Oxygen Reduction Catalyst.

To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.

Fe-Regulated Amorphous-Crystal Ni(Fe)P2 Nanosheets Coupled with Ru Powerfully Drive Seawater Splitting at Large Current Density.

Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P2 nanosheet bifunctional catalyst (Ru-Ni(Fe)P2 /NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P2 , and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P2 /NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm-2 for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO2 /NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm-2 and 600 mA cm-2 for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.

Flower-Like Amorphous MoO3- x Stabilized Ru Single Atoms for Efficient Overall Water/Seawater Splitting.

Benefitting from the maximum atom utilization efficiency, special size quantum effects and tailored active sites, single-atom catalysts (SACs) have been promising candidates for bifunctional catalysts toward water splitting. Besides, due to the unique structure and properties, some amorphous materials have been found to possess better performance than their crystalline counterparts in electrocatalytic water splitting. Herein, by combining the advantages of ruthenium (Ru) single atoms and amorphous substrates, amorphous molybdenum-based oxide stabilized single-atomic-site Ru (Ru SAs-MoO3- x /NF) catalysts are conceived as a self-supported electrode. By virtue of the large surface area, enhanced intrinsic activity and fast reaction kinetics, the as-prepared Ru SAs-MoO3- x /NF electrode effectively drives both oxygen evolution reaction (209 mV @ 10 mA cm-2 ) and hydrogen evolution reaction (36 mV @ 10 mA cm-2 ) in alkaline media. Impressively, the assembled electrolyzer merely requires an ultralow cell voltage of 1.487 V to deliver the current density of 10 mA cm-2 . Furthermore, such an electrode also exhibits a great application potential in alkaline seawater electrolysis, achieving a current density of 100 mA cm-2 at a low cell voltage of 1.759 V. In addition, Ru SAs-MoO3- x /NF only has very small current density decay in the long-term constant current water splitting test.

Effect of B-Doping and Manifestation on TiO2-Supported IrO2 for Oxygen Evolution Reaction in Water Electrolysis.

To commercialize hydrogen production by proton exchange membrane (PEM) electrolysis, the amount of rare and precious metal (iridium) required for anodic oxygen evolution reaction (OER) must be greatly reduced. In order to solve the problem, carrier loading is used to reduce the amount of iridium. Unlike the carrier modified by conventional metal element doping, this work doped the carrier with the nonmetallic element and then prepared IrO2/TiBxO2 composite catalyst using the Adams melting method. B-doped TiO2 supports with different doping amounts show the main phase rutile structure. Among them, the conductivity of B-doped carrier shows an increasing trend with the increase of doping amount, because boron can form holes and negative centers after doping, and more carriers improve the conductivity of the support. In addition, since element B is manifested from inside to outside on the support, B can affect the catalytic process. After the manifestation of element B, the carrier loaded with IrO2 exhibited superior electrocatalytic properties. The voltammetric charge per unit mass of 40IrO2/TiB0.3O2#2 (where #2 represents B after manifestation) reaches 1970 mC (cm2 mg)-1, the corresponding overpotential is 273 mV at a current density of 10 mA/cm-2, and the Tafel slope is 61.9 mV/dec Also, the charge transfer resistance is only 15 Ω. Finally, in the stability test, the composite catalyst is also better than pure IrO2 in the 20 000 s operation. Therefore, element B has an unexpectedly positive effect on the catalytic progress on the surface of the support after its manifestation.

Altered electronic structure of trimetallic FeNiCo-MOF nanosheets for efficient oxygen evolution.

Theoretical calculation results unveil that the reconstructed Co(Ni)OOH on FeNiCo-MOF during OER processes is beneficial to improve the OER activity. Experimentally, to achieve 2D trimetallic FeNiCo-MOF nanosheets, a facile room-temperature dispersion approach is employed. Such 2D nanosheets reveal an OER overpotential as low as 239 mV at 10 mA cm-2 and excellent long-term stability in 1M KOH. Undoubtedly, this work highlights the great potential of directly utilizing MOF nanosheets as OER electrocatalysts.

Fe-Incorporated Ni/MoO2 Hollow Heterostructure Nanorod Arrays for High-Efficiency Overall Water Splitting in Alkaline and Seawater Media.

Developing high-efficiency and cost-effective bifunctional catalysts for water electrolysis is fascinating but still remains challenging. Thus, diverse strategies have been utilized to boost the activity toward oxygen/hydrogen evolution reactions (OER/HER) for water splitting. Among them, composition and structure engineering as an effective strategy has received extensive attention. Here, by means of a self-sacrificing template strategy and simultaneous regulation of the composition and structure, Fe-incorporated Ni/MoO2 heterostructural (NiFe/Fe-MoO2 ) hollow nanorod arrays are designed and constructed. Benefiting from abundant catalytic active sites, high intrinsic activity, and fast reaction kinetics, NiFe/Fe-MoO2 exhibits superior OER (η20  = 213 and 219 mV) and Pt-like HER activity (η10  = 34 and 38 mV), respectively, in 1 m KOH and alkaline seawater media. This results in attractive prospects in alkaline water and seawater electrolysis with only voltages of 1.48 and 1.51 V, and 1.69 and 1.73 V to achieve current densities of 10 and 100 mA cm-2 , respectively, superior to the Pt/C and RuO2 pair as a benchmark. Undoubtedly, this work provides a beneficial approach to the design and construction of noble-metal-free bifunctional catalysts toward efficient hydrogen production from alkaline water and seawater electrolysis.

Competitive Coordination-Pairing between Ru Clusters and Single-Atoms for Efficient Hydrogen Evolution Reaction in Alkaline Seawater.

The coordination environment of Ru centers determines their catalytic performance, however, much less attention is focused on cluster-induced charge transfer in a Ru single-atom system. Herein, by density functional theory (DFT) calculations, a competitive coordination-pairing between Ru clusters (RuRu bond) and single-atoms (RuO bond) is revealed leading to the charge redistribution between Ru and O atoms in ZnFe2 O4 units which share more free electrons to participate in the hydrogen desorption process, optimizing the proton adsorption and hydrogen desorption. Thus, a clicking confinement strategy for building a competitive coordination-pairing between Ru clusters and single-atoms anchored on ZnFe2 Ox nanosheets over carbon via RuO ligand (Ru1, n -ZnFe2 Ox -C) is proposed. Benefiting from the optimized coordination effect and the electronic synergy between Ru clusters and single-atoms, such a catalyst demonstrates the excellent activity and excellent stability in alkaline and seawater media, which has exceptional hydrogen evolution reaction activity with overpotentials as low as 10.1 and 15.9 mV to reach the current density of 10 mA cm-2 in alkaline and seawater media, respectively, higher than that of commercial Pt/C catalysts as a benchmark. Furthermore, it owns remarkably outstanding mass activity, approximately 2 and 8 times higher than that of Pt catalysts in alkaline and seawater media, respectively.

Ni-soc-MOF derived carbon hollow sphere encapsulated Ni3Se4 nanocrystals for high-rate supercapacitors.

Carbon hollow sphere encapsulated Ni3Se4 (Ni3Se4@CHS) nanocrystals are prepared using the Ni-soc-MOF by pyrolysis and further selenization. Ni3Se4@CHS exhibits a capacitance of 1720 F g-1 at 1 A g-1 and a capacitance retention of 97% after 6000 cycles at 5 A g-1. Moreover, the asymmetric supercapacitor of Ni3Se4@CHS//AC displays a wide potential window of 1.6 V, an energy density of 45.2 W h kg-1 at a power density of 800 W kg-1, and excellent cycling stability (89% capacitance retention) after 5000 cycles. Overall, this work establishes a significant step to synthesize a new carbon-based material with appreciable capacitance and long cycling durability for potential applications in energy storage and beyond.

Work-function-induced Interfacial Built-in Electric Fields in Os-OsSe2 Heterostructures for Active Acidic and Alkaline Hydrogen Evolution.

Theoretical calculations unveil that the formation of Os-OsSe2 heterostructures with neutralized work function (WF) perfectly balances the electronic state between strong (Os) and weak (OsSe2 ) adsorbents and bidirectionally optimizes the hydrogen evolution reaction (HER) activity of Os sites, significantly reducing thermodynamic energy barrier and accelerating kinetics process. Then, heterostructural Os-OsSe2 is constructed for the first time by a molten salt method and confirmed by in-depth structural characterization. Impressively, due to highly active sites endowed by the charge balance effect, Os-OsSe2 exhibits ultra-low overpotentials for HER in both acidic (26 mV @ 10 mA cm-2 ) and alkaline (23 mV @ 10 mA cm-2 ) media, surpassing commercial Pt catalysts. Moreover, the solar-to-hydrogen device assembled with Os-OsSe2 further highlights its potential application prospects. Profoundly, this special heterostructure provides a new model for rational selection of heterocomponents.

Inhibiting Mn Migration by Sb-Pinning Transition Metal Layers in Lithium-Rich Cathode Material for Stable High-Capacity Properties.

Owing to the interacted anion and cation redox dynamics in Li2 MnO3 , the high energy density can be obtained for lithium-rich manganese-based layered transition metal (TM) oxide [Li1.2 Ni0.2 Mn0.6 O2 , LNMO]. However, irreversible migration of Mn ions and oxygen release during highly de-lithiation can destroy its layered structure, leading to voltage and capacity decline. Herein, non-TM antimony (Sb) is pinned to the TM layer of LNMO by a facile sol-gel method. High-resolution ex and in situ characterization technologies manifest that the introduction of trace Sb inhibits the migration of Mn ions, forming a more stable structure. Sb can impressively adjust the Mn-O interaction between anions and cations, beneficial to decrease the energy level of Mn 3d and O 2p orbitals and expand their band gap according to the  theoretical calculation results. As a result, the discharge specific capacity and the energy density for SbLi1.2 [Ni0.2 Mn0.6 ]O2 (SLNMO) reaches as high as 301 mAh g-1 and 1019.6 Wh kg-1 at 0.1 C, respectively. Moreover, the voltage decay is reduced by 419.8 mV compared with LNMO. The regulative interaction between Mn 3d and isolated O 2p bands provides an accurate guidance for solving electrochemical performance deficiencies of lithium-rich manganese-based cathode oxide.