Iron Oxide Nanoparticles Engineered Macrophage-Derived Exosomes for Targeted Pathological Angiogenesis Therapy.

Engineering exosomes with nanomaterials usually leads to the damage of exosomal membrane and bioactive molecules. Here, pathological angiogenesis targeting exosomes with magnetic imaging, ferroptosis inducing, and immunotherapeutic properties is fabricated using a simple coincubation method with macrophages being the bioreactor. Extremely small iron oxide nanoparticle (ESIONPs) incorporated exosomes (ESIONPs@EXO) are acquired by sorting the secreted exosomes from M1-polarized macrophages induced by ESIONPs. ESIONPs@EXO suppress pathological angiogenesis in vitro and in vivo without toxicity. Furthermore, ESIONPs@EXO target pathological angiogenesis and exhibit an excellent T1-weighted contrast property for magnetic resonance imaging. Mechanistically, ESIONPs@EXO induce ferroptosis and exhibit immunotherapeutic ability toward pathological angiogenesis. These findings demonstrate that a pure biological method engineered ESIONPs@EXO using macrophages shows potential for targeted pathological angiogenesis therapy.

Silver Nanowires Cascaded Layered Double Hydroxides Nanocages with Enhanced Directional Electron Transport for Efficient Electrocatalytic Oxygen Evolution.

Designing and fabricating highly efficient oxygen evolution reaction (OER) electrocatalytic materials for water splitting is a promising and practical approach to green and sustainable low-carbon energy systems. Herein, a facile in situ growth self-template strategy by using ZIF-67 as a consumable layered double hydroxides (LDHs) template and silver nanowires (AgNWs) as 1D conductive cascaded substrate to controllably synthesize the target AgNWs@CoFe-LDH composites with unique hollow shell sugar gourd-like structure and enhanced directional electron transport effect is reported. The AgNWs exhibit the key functions of the close connection of CoFe-LDH nanocages and the support of the directional electron transport effect in the composite catalyst inducing electrons directionally moving from CoFe-LDH to AgNWs. Meanwhile, the CoFe-LDH nanocages with ultrathin nanosheets and hollow structural properties show abundant active sites for electrocatalytic oxygen generation. The versatile AgNWs@CoFe-LDH catalyst with optimized components, enhanced directional electron transport, and synergistic effect achieves high OER performance with the overpotential of 207 mV and long-term 50 h stability at 10 mA cm-2 in an alkaline medium. Moreover, in-depth insights into the microstructure, structure-activity relationships, identification of key intermediate species, and a proton-coupled four-electron OER mechanism based on experimental discovery and theoretical calculation are also demonstrated.

Matrix-type bismuth-modulated copper-sulfur electrode using local photothermal effect strategy for efficient seawater splitting.

Constructing catalytic electrodes with green economy, stability, and high efficiency is crucial for achieving overall economic water splitting. Herein, a matrix-type bismuth-modulated nickel-boron electrodes loaded on sulfurized copper foils (Bi-NiBx@CFS) is synthesized via in situ mild electroless plating. This electrode features a 2-dimensional (2D) matrix-type nanosheet structure with uniform, large pores, providing more active sites and ensuring a high gas transmission rate. Notably, the crystalline-amorphous structure constituted by the photothermal materials Bi and NiBx is loaded onto sulfide-based heterostructures. This enhances the catalytic activity through the "local photothermal effect" strategy. A performance enhancement of approximately 10 % is achieved for the Bi-NiBx@CFS at a current density of 10 mA cm-2 using this strategy at 298 K. This enhancement is equivalent to increasing the temperature of conventional electrolyte solutions by 321 K. In addition, the overpotential required to catalytically drive seawater splitting at the same current density is only 1.486 V. The Bi-NiBx@CFS electrode operates stably for 200 h without any performance degradation at industrial-grade current densities. The Bi-NiBx@CFS electrode under the "localized photothermal effect" strategy is expected to be a new type of electrocatalyst for overall seawater splitting.

Tuning electronic structure of hedgehog-like nickel cobaltite via molybdenum-doping for enhanced electrocatalytic oxygen evolution catalysis.

As a typical spinel oxide, nickel cobaltite (NiCo2O4) is considered to be a promising and reliable oxygen evolution reaction (OER) catalyst due to its abundant oxidation states and the synergistic effect of multiple metal species. However, the electrocatalytic OER performance of NiCo2O4 has always been limited by the low specific surface area and poor intrinsic conductivity of spinels. Herein, the hedgehog-like molybdenum-doped NiCo2O4 (Mo-NiCo2O4) catalyst was prepared as an efficient OER electrocatalyst via a facile hydrothermal method followed with high-temperature annealing. The Mo-NiCo2O4-0.075 with Mo doping concentration of âˆ¼ 1.95 wt% exhibits excellent OER performance with a low overpotential of 265 mV at a current density of 10 mA·cm-2and a Tafel slope of 126.63 mV·dec-1, as well as excellent cyclingstability.The results demonstrated that the hedgehog-like structure provides Mo-NiCo2O4 with the high surface area and mesopores that enhance electrolyte diffusion and optimal active site exposure. The in-situ Raman spectra and density functional theory calculations show that the Mo cations doping improve the intrinsic conductivity of the NiCo2O4 while modulating the chemisorption of intermediates. Meanwhile, the energy barriers of *OH and O* formation decrease significantly after Mo doping, effectively facilitating water dissociation and optimizing the reaction kinetics.

Corrosion resistance and earth-abundance FeS-based heterojunction catalyst for seawater splitting at industrial grade density.

The strategic progression toward highly efficient transition metal electrocatalytic electrodes is crucial to achieving efficiency and long-term stability in hydrogen production from authentic seawater sources. This work reports the development of a self-supporting, heterogeneous and corrosion-resistant iron sulfur-based catalytic electrode via a streamlined, one-step process involving sulfide etching and electroless plating on an iron foam substrate (IF). This new electrode, named NiS-FeS@IF, involves a nanostructured NiS-FeS catalytic material that combines in situ, resulting in a thin, ultrathin nanospherical layer on the IF. This construction has low overpotentials of merely 322 mV for the hydrogen evolution reaction (HER) and 563 mV for the oxygen evolution reaction (OER) with a current density of 500 mA cm-2 in alkaline simulated seawater electrolytes. Importantly, the NiS-FeS@IF electrode enduring more than 500 h at an industrial grade high current density of 1 A cm-2 without noteworthy performance deterioration. The unique and uniformly dispersed morphology of NiS-FeS facilitates intensified interfacial electron transfer, optimizes active site exposure and provides efficient channels for the rapid release and mass transfer of gas bubbles. This work introduces a novel approach for the facile preparation of efficient electrode materials.

In situ fabrication of sporoid-like flexible electrodes via Fe-regulated electron density for highly efficient and ultra-stable overall seawater splitting.

Construction of ultra-stable, flexible, efficient and economical catalytic electrodes is of great significance for the seawater electrolysis for hydrogen production. This work is grounded in a one-step mild electroless plating method to construct industrial-grade super-stable overall water splitting (OWS) catalytic electrodes (Fe1-Ni1P@GF) by growing loose and porous spore-like Fe1-Ni1P conductive catalysts in situ on flexible glass fibre (GF) insulating substrates with precise elemental regulation. Cost-effective Fe regulation boosts the electronic conductivity and charge transfer ability to achieve the construction of high intrinsic activity and strong electron density electrodes. Fe1-Ni1P@GF exhibits remarkable catalytic performance in hydrogen and oxygen evolution reaction (HER and OER), providing current densities of 10 mA cm-2 for HER and 100 mA cm-2 for OER at overpotentials of 51 and 216 mV, respectively. Moreover, it achieves 10 mA cm-2 at 1.42 V for OWS, and exhibits stable operation for over 1440 h at 1000 mA cm-2 in quasi-industrial environment of 6.0 M KOH + 0.5 M NaCl, without any performance degradation. This strategy enables the preparation of universally applicable P-based electrodes (ternary, quaternary, etc.) and large-area flexible electrodes (paper or cotton), significantly expands the practicality of the electrodes and demonstrating promising potential for industrial applications.

Lipid nanoparticle-mediated delivery of IL-21-encoding mRNA induces viral clearance in mouse models of hepatitis B virus persistence.

Hepatitis B virus (HBV) covalently closed circular DNA (cccDNA), the transcription template for all viral mRNAs, is highly stable and current treatment options cannot effectively induce its clearance. Previously, we established an HBV persistence mouse model based on a clinical isolate (termed BPS) and identified interleukin-21 (IL-21) as a potent inducer of HBV clearance. Lipid nanoparticle (LNP) mediated delivery of mRNA has proven to be a highly safe and effective delivery platform. This work explored the applicability and effectiveness of the mRNA-LNP platform in IL-21-based HBV therapies. First, LNP-encapsulated murine IL-21 mRNA (LNP-IL-21) was prepared, characterized, and demonstrated to engender IL-21 expression in vitro and in vivo. Next, LNP-IL-21 was shown to induce clearance of both serum and intrahepatic HBV antigen and DNA in two HBV persistence mouse models based on BPS and recombinant cccDNA (rcccDNA), respectively, which was associated with HBV-specific humoral and cellular immune responses. Furthermore, peripheral blood mononuclear cells from BPS persistence mice treated ex vivo with LNP-IL-21 and HBV surface antigen (HBsAg) could induce similar HBV clearance upon infusion into recipient mice. These findings indicated that IL-21 combined with mRNA-LNP platform represents a valid and promising strategy for developing novel therapeutics against chronic HBV infection.

NaCl template-assisted construction of a CoP-MoP heterostructured electrocatalyst for electrocatalytic nitrogen reduction.

The electrocatalytic nitrogen reduction reaction (NRR) to ammonia is a promising technology to store renewable energy and mitigate greenhouse gas emissions. However, it usually suffers from low ammonia yield and selectivity because of the lack of efficient electrocatalysts. Herein, we report that the construction of metal phosphide heterojunctions is an efficient strategy for NRR activity enhancement. A CoP-MoP heterojunction electrocatalyst, which is fabricated by a facile NaCl template-assisted strategy, exhibits a favorable ammonia yield rate of 77.8 µg h-1 mgcat-1 (38.9 µg h-1 cm-2) and a high faradaic efficiency of 11.16% at -0.50 V versus the reversible hydrogen electrode. The high NRR electrocatalytic activity can be attributed to the electronic coupling effects and interfacial synergistic effects of CoP and MoP at the heterojunction interface, which accelerates the electron transfer rate. Moreover, Mo doping changes the d-band centers of metal sites on the CoP surface, which is conducive to N2 adsorption and promotes N2* adsorption in the competition of occupying active sites, thus inhibiting the HER. This work manifests the high potential of phosphide electrocatalysts and opens an alternative route toward NRR electrocatalysis.

WOx nanoparticles coupled with nitrogen-doped porous carbon toward electrocatalytic N2 reduction.

The electrocatalytic nitrogen reduction reaction (eNRR) is a sustainable and green alternative to the traditional Haber-Bosch process. However, the chemical inertness of nitrogen gas and the competitive hydrogen evolution reaction significantly limit the catalytic performance of eNRR. Although tungsten oxide-based eNRR catalysts could donate unpaired electrons to the antibonding orbitals of N2 and accept lone electron pairs from N2 to dissociate NN triple bonds, the low electrical conductivity and the influence of the variable valence of W still affect the catalytic activity. Herein, a high-performance eNRR catalyst WOx nanoparticle/nitrogen-doped porous carbon (WOx/NPC) was prepared by a one-step thermal pyrolysis method. The results reveal that WOx gradually changes from the dominant WO2 phase to the WO3 phase. WOx/NPC-700 °C with WO2 NPs anchored on the surfaces of NPC via W-N bonding could deliver a high NH3 yield of 46.8 µg h-1 mg-1 and a high faradaic efficiency (FE) of 10.2%. The edge W atomic site on WOx/NPC is demonstrated to be the active center which could activate a stable NN triple bond with an electron-donating ability. Benefiting from the covalent interaction between the WOx nanoparticles and NPC, WOx/NPC also shows high electrocatalytic stability.

CDs Regulated Sulfur-Based Flexible Electrode with Range pH Values for Efficient and Durable Hydrogen Evolution Reaction.

How to mildly structure a high intrinsic activity and stable catalytic electrode to realize long-term catalytic water splitting to produce hydrogen at a wide range of pH values at industrial high current is a challenge. Herein, this work creatively proposes to prepare industrial-grade catalytic electrodes with high efficiency and stability at high current density through carbon quantum dots (CDs) modification nickel sulfide on hydrophilic flexible filter paper via one-step mild chemical plating (denoted as CDs-Ni3 S2 @HFP). The intrinsic activity and surface area, electron transfer ability, and corrosion resistance of Ni3 S2 material are increased due to the regulation, homogenous, and high concentration doping of CDs. The overpotential of the flexible catalytic electrode is only 30, 35, and 87 mV in 1 m KOH, simulated seawater (1 m KOH + 0.5 m NaCl), and neutral electrolyte (0.5 m PBS) at a current density of 10 mA cm-2 . More attractively, the CDs-Ni3 S2 @HFP electrode achieves over 500 h of efficient and stable catalysis at industrial high current density (500 mA cm-2 ). Due to the advantages of mild, universal, and large-area preparation of catalytic materials, this work provides technical support for flexible catalytic electrodes in efficient catalysis toward water splitting, energy storage, and device preparation.

Fabrication of ultra-stable and high-efficient CoP-based electrode toward seawater splitting at industrial-grade current density.

The mild and rapid construction of economical, efficient and ultrastable electrodes for hydrogen production via water splitting at industrial-grade current density remains extremely challenging. Herein, a one-step mild electroless plating method is proposed to deposit cobalt phosphorus (CoP)-based species on robust nickel net (NN, denoted as Co-P@NN). The tight interfacial contact, corrosion-proof self-supporting substrate and synergistic effect of Co-P@Co-O contribute greatly to the rapid electron transport, high intrinsic activity and long-term durability in the alkaline simulated seawater (1.0 M KOH + 0.5 M NaCl). Attractively, Co-P@Co-O also achieves ultrastable catalysis for over 2880 h with negligible activity attenuation under various alkaline extreme conditions (simulated seawater, high-salt environment, domestic sewage and so on). Furthermore, this work successfully constructs a series of ternary elemental doped (Ni, S, B, Fe and so on) CoP-based catalytic electrodes for highly efficient overall seawater splitting (OSWS). This work demonstrates not only an ideal platform for the versatile strategy of mildly obtaining CoP-based electrocatalysts but also the pioneering philosophy of large-scale hydrogen production.

Recent Advances of Photoactive Near-Infrared Carbon Dots in Cancer Photodynamic Therapy.

Photodynamic therapy (PDT) is a treatment that employs exogenously produced reactive oxygen species (ROS) to kill cancer cells. ROS are generated from the interaction of excited-state photosensitizers (PSs) or photosensitizing agents with molecular oxygen. Novel PSs with high ROS generation efficiency is essential and highly required for cancer photodynamic therapy. Carbon dots (CDs), the rising star of carbon-based nanomaterial family, have shown great potential in cancer PDT benefiting from their excellent photoactivity, luminescence properties, low price, and biocompatibility. In recent years, photoactive near-infrared CDs (PNCDs) have attracted increasing interest in this field due to their deep therapeutic tissue penetration, superior imaging performance, excellent photoactivity, and photostability. In this review, we review recent progress in the designs, fabrication, and applications of PNCDs in cancer PDT. We also provide insights of future directions in accelerating the clinical progress of PNCDs.

Quantum dot-doped CeOx-NiB with modulated electron density as a highly efficient bifunctional electrocatalyst for water splitting.

Development of economical, efficient and durable non-noble metal electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) holds great promise, but still faces great challenges. Herein, a strategy of doping metal borides with rare earth metal oxides and introducing silicon carbide (SiC) quantum dots has been explored to develop efficient bifunctional electrocatalysts. A novel electrocatalyst consists of SiC quantum dot-decorated CeOx-NiB supported on nickel foam via a one-step mild electroless plating reaction (denoted as CeOx-NiB/SiC@NF). Notably, the modulated electron density of the CeOx-NiB/SiC@NF electrode significantly boosts the electrochemically active surface area and electron transfer, and optimizes the hydrogen/water absorption free energy, which delivers current densities of 50 mA cm-2 and 10 mA cm-2 at overpotentials of only 131 mV and 234 mV for the HER and the OER, respectively. The target electrode requires only 1.43 V to provide 10 mA cm-2 for overall water splitting in 1.0 M KOH. Moreover, the electrode also exhibits good stability and durability at the industrial-grade current density (0.5-1 A cm-2). This work provides a new idea for the development of efficient and durable non-precious metal catalysts.

Exosomes incorporated with black phosphorus quantum dots attenuate retinal angiogenesis via disrupting glucose metabolism.

Black phosphorus quantum dots (BPQDs) have shown potential in tumor therapy, however, their anti-angiogenic functions have not been studied. Although BPQDs are easily degraded to non-toxic phosphrous, the reported toxicity, poor stability, and non-selectivity largely limit their further application in medicine. In this study, a vascular targeting, biocompatible, and cell metabolism-disrupting nanoplatform is engineered by incorporating BPQDs into exosomes modified with the Arg-Gly-Asp (RGD) peptide (BPQDs@RGD-EXO nanospheres, BREs). BREs inhibit endothelial cells (ECs) proliferation, migration, tube formation, and sprouting in vitro. The anti-angiogenic role of BREs in vivo is evaluated using mouse retinal vascular development model and oxygen-induced retinopathy model. Combined RNA-seq and metabolomic analysis reveal that BREs disrupt glucose metabolism, which is further confirmed by evaluating metabolites, ATP production and the c-MYC/Hexokinase 2 pathway. These BREs are promising anti-angiogenic platforms for the treatment of pathological retinal angiogenesis with minimal side effects.

Construction of Non-Precious Metal Self-Supported Electrocatalysts for Oxygen Evolution from a Low-Temperature Immersion Perspective.

Water splitting is considered as a promising technology to solve energy shortage and environmental pollution. Since oxygen evolution reaction (OER) directly affects the efficiency of hydrogen evolution, the preparation of efficient and inexpensive OER catalysts is an urgent problem. "Low-temperature immersion" (LTI) is expected to be a prospective strategy for electrocatalyst preparation due to its simplicity and energy-saving advantages. However, there is almost no comprehensive overview on the progress of LTI engineering in the construction of non-precious metal self-supported electrocatalysts for OER. Herein, this review firstly introduces the principles and applications of LTI engineering-assisted preparation of non-precious metal self-supported electrocatalysts in terms of etching and deposition. Then the mechanism of OER is analyzed from an amorphous viewpoint, and finally some perspective insights and future challenges of this method are discussed.

Mild construction of an Fe-B-O based flexible electrode toward highly efficient alkaline simulated seawater splitting.

It is essential to construct self-supporting electrodes based on earth-abundant iron borides in a mild and economical manner for grid-scale hydrogen production. Herein, a series of highly efficient, flexible, robust, and scalable Fe-B-O@FeBx modified on hydrophilic cloth (denoted as Fe-B-O@FeBx/HC, 10 cm × 10 cm) are fabricated by mild electroless plating. The overpotentials and Tafel slope values for the hydrogen and oxygen evolution reactions are 59 mV and 57.62 mV dec-1 and 181 mV and 65.44 mV dec-1, respectively; only 1.462 V is required to achieve 10 mA cm-2 during overall water splitting (OWS). Fe-B-O@FeBx/HC maintains its high catalytic activity for more than 7 days at an industrial current density (400 mA cm-2), owing to the loosened popcorn-like Fe-B-O@FeBx that is firmly loaded on a 2D-layered and mechanically robust substrate along with its fast charge and mass transfer kinetics. The chimney effect of core-shell borides@(oxyhydro)oxides enhances the OWS performance and protects the inner metal borides from further corrosion. Moreover, the flexible Fe-B-O@FeBx/HC electrode has a low cost for grid-scale hydrogen production ($2.97 kg-1). The proposed strategy lays a solid foundation for universal preparation, large-scale hydrogen production and practical applications thereof.

Fabrication of Ultra-Durable and Flexible NiPx -Based Electrode toward High-Efficient Alkaline Seawater Splitting at Industrial Grade Current Density.

Designing nonprecious metal-based electrocatalysts to yield sustainable hydrogen energy by large-scale seawater electrolysis is challenging to global emissions of carbon neutrality and carbon peaking. Herein, a series of highly efficient, economical, and robust Ni-P-based nanoballs grown on the flexible and anti-corrosive hydrophobic asbestos (NiPx @HA) is synthesized by electroless plating at 25 °C toward alkaline simulated seawater splitting. On the basis of the strong chemical attachment between 2D layered substrate and nickel-rich components, robust hexagonal Ni5 P4 crystalline modification, and fast electron transfer capability, the overpotentials during hydrogen/oxygen evolution reaction (HER/OER) are 208 and 392 mV at 200 mA cm-2 , and the chronopotentiometric measurement at 500 mA cm-2 lasts for over 40 days. Additionally, the versatile strategy is broadly profitable for industrial applications and enables multi-elemental doping (iron/cobalt/molybdenum/boron/tungsten), flexible substrate employment (nickel foam/filter paper/hydrophilic cloth), and scalable synthesis (22 cm × 22 cm). Density functional theory (DFT) also reveals that the optimized performance is due to the fundamental effect of incorporating O-source into Ni5 P4 . Therefore, this work exhibits a complementary strategy in the construction of NiPx -based electrodes and offers bright opportunities to produce scalable hydrogen effectively and stably in alkaline corrosive electrolytes.

Mild Construction of "Midas Touch" Metal-Organic Framework-Based Catalytic Electrodes for Highly Efficient Overall Seawater Splitting.

Mild construction of highly efficient and durable practical electrodes for overall water splitting (OWS) at industrial-grade current density is currently a significant challenge. Herein, metal-organic framework (MOF) materials are grown in situ on the surface of carbon cloth (CC) at 25 °C, and quickly "interspersed" by cobalt-boron (Co-B) via electroless plating for 30 min to obtain a highly efficient and stable CoB@MOF@CC self-supporting electrode. Owing to the large specific surface area, abundant active sites, and porous structure, the MOF-based CC modified by bamboo leaf-like ultrathin CoB has remarkable electrochemical catalysis efficiency. The CoB@MOF@CC electrode exhibits excellent performance during the hydrogen evolution reaction (η10  = 57 mV, η500  = 266 mV) and oxygen evolution reaction (η10  = 209 mV, η500  = 423 mV) in alkaline simulated seawater, and is durable for 2500 h at 500 mA cm-2 . The OWS performance is obviously enhanced by employing the prepared electrode, which only requires 1.49 V to achieve 10 mA cm-2 and is durable for over 360 h at industrial-grade current densities in alkaline high-salt, real seawater, rainwater, and urea electrolytes.

Mild construction of robust FeS-based electrode for pH-universal hydrogen evolution at industrial current density.

The development of fast and mild preparation of transition metal electrocatalysts for efficient and ultra-stable water electrolysis in wide pH range electrolytes is essential for hydrogen energy supply. Herein, ultrathin and metastable FeS nanolayer self-supported on 3D porous iron foam (IF) substrate is fabricated via one-step mild sulfurization etching for only 2 h to obtain FeS@IF electrode, which achieves efficient and long-term hydrogen evolution in alkaline simulated seawater (1.0 M KOH + 0.5 M NaCl), neutral electrolyte (1.0 M PBS) and other corrosive systems. The overpotentials are only 63 mV and 78 mV to drive 10 mA cm-2 during hydrogen evolution in 1.0 M KOH + 0.5 M NaCl and 1.0 M PBS, respectively. Additionally, the FeS@IF electrode continuously catalyzes for over 600 h at 0.2-0.4 A cm-2 in 1.0 M PBS with negligible performance loss, partly attributed to FeS nanolayer firmly etching on the surface and the formation of corrosion-resistant ultrathin nano fan-like iron sulfide oxide (FeOxSy). This uniformly-distributed morphology helps to facilitate the interfacial electron transmission between active species and substrate, expose more active sites, and provide moderate channels for the rapid liberation of gas bubbles and mass transfer. This work proposes a novel strategy for developing efficient and stable catalysts for hydrogen production in wide pH range systems.

Composition Engineering of Amorphous Nickel Boride Nanoarchitectures Enabling Highly Efficient Electrosynthesis of Hydrogen Peroxide.

Developing advanced electrocatalysts with exceptional two electron (2e- ) selectivity, activity, and stability is crucial for driving the oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2 O2 ). Herein, a composition engineering strategy is proposed to flexibly regulate the intrinsic activity of amorphous nickel boride nanoarchitectures for efficient 2e- ORR by oriented reduction of Ni2+ with different amounts of BH4 - . Among borides, the amorphous NiB2 delivers the 2e- selectivity close to 99% at 0.4 V and over 93% in a wide potential range, together with a negligible activity decay under prolonged time. Notably, an ultrahigh H2 O2 production rate of 4.753 mol gcat -1 h-1 is achieved upon assembling NiB2 in the practical gas diffusion electrode. The combination of X-ray absorption and in situ Raman spectroscopy, as well as transient photovoltage measurements with density functional theory, unequivocally reveal that the atomic ratio between Ni and B induces the local electronic structure diversity, allowing optimization of the adsorption energy of Ni toward *OOH and reducing of the interfacial charge-transfer kinetics to preserve the OO bond.