Abundant Phosphorus Research Articles

Phosphorus fractions and their vertical distribution in seabed sediments of the eastern Baltic Sea

Phosphorus fractions and their vertical distribution in seabed sediments were studied in short cores from four coastal sites of western Estonia (Western Gulf of Finland, Väinameri Sea, Suur Strait, and Gulf of Riga) representing accumulation and erosion/transport settings. As a result of recent large-scale discharges of nutrients into the marine environment, abundant phosphorus has accumulated in the seabed sediments, from where it can, under the expansion of hypoxic or anoxic conditions, be remobilized and released back into the water column. A sequential extraction method with a neutral, a reducing, a basis, and an acidic solution was used to evaluate the distribution of phosphorous in pools of five different carrier fractions. Potentially mobile phosphorus is mostly associated with redox-sensitive iron- and manganese oxyhydroxides, and this fraction is significant in the Western Gulf of Finland and the Gulf of Riga. As oxygen conditions gradually deteriorate, the remobilization of a considerable amount of potentially mobile phosphorus from sediments can affect the entire Baltic Sea ecosystem.

Facile constructing ZrO2 nanoparticles equipped with high conductivity carbon networks as pseudocapacitive anodes for removing phosphorus

Phosphorus pollution can seriously disrupt water quality and endanger ecosystem sustainability. Nonetheless, a few typical methods have been employed to remove phosphorus, but there are still challenges in controlling phosphorus from sewage. Capacitive deionization (CDI) displays the merits of having eco-friendliness and low energy consumption when capturing phosphorus. However, traditional carbon electrodes often suffer from the limitation that phosphorus uptake sites are insufficient. Herein, a novel ZrO2 nanoparticle equipped with a highly conductive carbon network (NZrC) was fabricated by a facile co-pyrolysis process. Na2EDTA can provide additional carbon backbones, N species, and metal chelation sites. Zr-MOF was applied as the ZrO2 precursor with abundant phosphorus trapping sites. The results suggested that Na2EDTA favors improving the ZrO2 dispersion, mesoporous channel formation, and pseudocapacitive behavior. NZrC-21 at 1.2 V displays low energy consumption and the optimal phosphorus uptake capacity of 10.99 mg P/g because of its rich mesoporous structure, abundant pyrrolic-N, graphitic-N, and ZrO2 active sites, and outstanding electrochemical properties. Furthermore, several key parameters were investigated for their effect on phosphorus removal performance. The mechanism revealed that hydrogen bonds, ligand exchange, and electrostatic attraction are the main uptake processes. This work presents a novel perspective for the facile construction and utilization of metal oxide nanoparticles equipped with a highly conductive carbon network for removing phosphorus.

Crystalline-dependent surface reconstruction at low applied potential region for enhanced oxygen evolution reaction

Alkaline water electrolysis is apreferred technology for large-scale green hydrogen production. For most active transition metal-based catalysts during anodic oxygen evolution reaction (OER), the atomic structure of the anodic catalysts’ surface often undergoes reconstruction to optimize the reaction path and enhance their catalytic activity. The design and maintenance of highly active sites during this reconstruction process remain critical and challenging for most OER catalysts. In this study, we explored the effects of crystal structures in pre-catalysts on surface reconstruction at low applied potential. Through experimental observation and theoretical calculation, we found out that catalysts with specific crystal structures exhibit superior surface remodeling ability, which enables them to better adapt to the conditions of the oxygen evolution reaction and achieve efficient catalysis. The discharge process enables the formation of abundant phosphorus vacancies on the surface, which in turn affects the efficiency of the entire oxygen evolution reaction. The optimized crystal structure of the catalyst results in an increase as high as 58.5 mA/cm2 for Ni5P4, which is twice as high as that observed for Ni2P. These results provide essential theoretical foundations and technical guidance for designing more efficient catalysts for oxygen evolution reactions.

Integrated Heterogeneous Engineering with the Vacancy Defect of Porous CoPv-MoxPv Nanosheets for an Accelerated Hydrogen Evolution Reaction.

Electrochemical water splitting is a possible way of realizing sustainable and clean hydrogen production but is challenging, because a highly active and durable electrocatalyst is essential. In this work, we integrated heterogeneous engineering and vacancy defect strategies to design and fabricate a heterostructure electrocatalyst (CoPv-MoxPv/CNT) with abundant phosphorus vacancies attached to carbon nanotubes (CNTs). The vacancy defects enabled the optimization of the electronic structure; thereby, the electron-rich low-valent metal sites enhanced the ability of nonmetallic P to capture proton H. Meanwhile, the heterogeneous interface between bimetallic phosphides and CNTs realized rapid electron transfer. In addition, the Co, Mo, and P active species in the electrocatalytic process exposed increased amounts of active sites featuring porous nanosheet structures, which facilitated the adsorption of reaction intermediates and thus enhanced the hydrogen evolution reaction performance. In particular, the optimized CoPv-MoxPv/CNT catalyst possesses an overpotential of 138 mV at a current density of 10 mA cm-2 and long-term stability for 24 h. This work offers insights and possibilities for the engineering and exploration of transition metal-based electrocatalysts through combining multiple synergistic strategies.

Microwave-assisted acidic hydrolysis of phytate from rye bran – Experimental procedure and model prediction

Phytate is an abundant phosphorus (P) compound in plant material, which cannot be taken up by monogastric animals but is to a significant part released into the environment with excreta. In order to make use of cereals' phytate content, phytate hydrolysis by microwave-assisted thermal treatment of an acidic rye bran extract into inorganic phosphate was investigated experimentally and by modelling for process application. A phytate conversion of 98.5% could be achieved at 200 °C and 15 min reaction time and showed to be highly dependent on the temperature by a sigmoidal correlation. Treatment time showed its main influence in the mid temperature range (between 150 and 180 °C), thus didn't play a role anymore at beginning hydrolysis and towards full conversion. A mathematical quartic model represented phytate conversion with an optimum at harshest examined conditions and allows for predictions of the hydrolysis within the parameter range investigated. A kinetic model gives parameters of reaction order 0.68 and an activation energy of 118.7 kJ/mol with the option to predict phytate hydrolysis beyond the investigated parameter range and for varying input concentration. Equal liberation of all six phosphate groups from phytate is mechanistically suggested. Both model approaches show comparable results.

Effects of Broccoli Rotation on Soil Microbial Community Structure and Physicochemical Properties in Continuous Melon Cropping

The limitations and weaknesses of continuous melon cropping have worsened in recent years. A melon–broccoli rotation can possibly alleviate the problems associated with melon monoculture; however, the underlying mechanisms and their impact on the rhizosphere’s soil microbial community remain unclear. Thus, high-throughput sequencing was used to evaluate the rhizosphere soil’s microbial community’s relative abundance and diversity under melon–broccoli rotation and continuous melon monoculture cropping systems. We found that relative fungal and bacterial diversity and richness increased while fungi relative abundances, such as Fusarium spp. were significantly decreased under broccoli rotation. During continuous cropping, enriched Acidobacteria and Streptomyces spp., Sphingomonas spp., and Pseudomonas spp. were identified, which play important roles in alleviating melon continuous cropping obstacles. The soil under continuous cropping was rendered acidic, underwent secondary salinization, rapidly accumulated soil organic carbon and nitrogen, and lost abundant phosphorus and potassium. In contrast, broccoli rotation partially mitigated these negative physicochemical responses. Redundancy analysis revealed that the soil pH, soil soluble salt content, and soil organic carbon were linked to structures of the soil bacterial and fungal community. Melon–broccoli rotation could effectively equilibrate the soil microenvironment and overcome the challenges and deficiencies associated with continuous melon cropping.

Ultrafast Microwave Synthesis of Ru-Doped MoP with Abundant P Vacancies as the Electrocatalyst for Hydrogen Generation in a Wide pH Range.

Molybdenum phosphide (MoP) has received increasing attention for the hydrogen evolution reaction (HER) due to its Pt-like electronic structure and high electrical conductivity. In this work, a flake-like Ru-doped MoP with phosphorus vacancy (Ru-MoP-PV) electrocatalyst is synthesized for the first time by a simple and rapid room-temperature microwave approach within 30 s. The created abundant phosphorus vacancies provide rich active sites and favor rapid electron transfer. The introduced Ru also enhances the catalytic activity of the synthesized electrocatalyst efficiently. Then, the designed Ru-MoP-PV possesses low overpotentials for HER with 79, 100, and 161 mV in 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline to obtain 10 mA cm-2. The Ru-MoP-PV and NiFe-layered double hydroxide are used as the cathode and the anode, respectively, to drive water splitting and just need a low cell voltage of 1.6 V to achieve 10 mA cm-2. This work provides a feasible way for the rapid production of metal phosphides for energy conversion and storage applications.

Synergy of phosphorus vacancies and build-in electric field into NiCo/NiCoP Mott-Schottky integrated electrode for enhanced water splitting performance

Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer, regulate adsorption energy of reaction intermediates, and provide additional active sites, which are regarded as valid means for improving catalytic activity. However, the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear. Herein, the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel (NF) has been synthesized through continuous phosphating and reduction processes. The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities, and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm2 in 1 mol/L KOH, respectively. Moreover, as both the cathode and anode of overall water splitting, the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm2, which are far exceeding the benchmark commercial electrodes. DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor, tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates. Furthermore, the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site, avoid catalyst shedding, thus improving the activity and structural stability of NiCo/NiCoP. This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.

NiFeZnP Nanosheets with Enriched Phosphorus Vacancies for Supercapattery Electrodes

Designing and fabricating outstanding electrode materials via simple preparation routes are viable ways for improving the performance of electrochemical supercapacitors. We report on the synthesis of NiFeZn phosphide interconnected nanosheets with abundant phosphorus vacancies (Pv-NiFeZnP) via a facile reduction route at room temperature. The fabricated Pv-NiFeZnP was fully characterized using energy-dispersive spectroscopy, field emission scanning electron microscopy, electron paramagnetic resonance, and X-ray photoelectron spectroscopy techniques. Owing to the porous interconnected nanosheet structure and the superior stability enabled by the direct binder-free growth on Ni foam, the Pv-NiFeZnP electrode, with optimized phosphorus vacancy formation, exhibits a superb electrochemical performance of 631.8 mC/cm2 (equivalent to 1579.5 mF/cm2), which is significantly higher than those reported in the literature. Also, the Pv-NiFeZnP||activated carbon asymmetric device exhibits a very high Coulombic efficiency (∼100%) and excellent long-term stability (98.8% capacity retention after 7500 cycles). The fabricated device can deliver 122.1 μWh/cm2 energy density at a power density of 750 μW/cm2. The fabricated NiFeZnP electrode is therefore a promising candidate for supercapacitor applications.

Selectively retaining nutrients in biochar in magnesium added two-zone staged copyrolysis of blue algae and corn gluten wastes

The disposal of blue algae (BA) and corn gluten (CG) wastes and the simultaneous recovery of abundant phosphorus (P) and nitrogen (N) by pyrolysis to obtain biochars with high fertility is a promising strategy. However, pyrolysis of BA or CG alone by a conventional reactor cannot reach the target. Herein, we propose a novel MgO-enhanced N and P recovery method by designing a two-zone staged pyrolysis reactor to highly efficiently recover N and P with easily available plant forms in BA and CG. The results show that a 94.58% total phosphorus (TP) retention rate was achieved by means of the special two-zone staged pyrolysis method, in which the effective P (Mg2PO4(OH) and R-NH-P) accounted for 52.9% of TP, while the total nitrogen (TN) reached 4.1 wt%. In this process, stable P was formed first at 400 °C to avoid rapid volatilization and then to form hydroxyl P at 800 °C. Meanwhile, Mg-BA char in the lower zone can efficiently absorb N-containing gas generated by the upper CG, forming dispersible N. This work is of great significance for improving the green utilization value of P and N in BA and CG.

Defect-rich Fe-doped Ni2P microflower with phosphorus vacancies as a high-performance electrocatalyst for oxygen evolution reaction

The development of efficient, durable, and low-cost non-noble metal-based electrocatalysts for the oxygen evolution reaction (OER) is crucial for the extensive application of water electrolysis, which is a sustainable technique for ultrapure hydrogen production. Herein, defect-rich Fe-doped Ni2P microflowers with abundant phosphorus vacancies (Fe-Ni2P-VP) are synthesized via a simple hydrothermal process, thermal phosphidation, and subsequent partial reduction method. The simultaneous introduction of Fe dopants and phosphorus vacancies in Fe-Ni2P-VP effectively reduce the charge transfer resistance and moderately adjust the electronic structure. Consequently, the Fe-Ni2P-VP exhibits high OER activity with a small overpotential of 289 mV to reach a current density of 10 mA cm−2, turnover frequency of 2.531 s−1 at a potential of 1.6 V vs. RHE, and low Tafel slope of 54.7 mV dec−1. Moreover, the long-term durability of Fe-Ni2P-VP is confirmed through chronopotentiometry tests over 100 h in an alkaline solution. This study provides new insights into the synthesis of noble-metal-free electrocatalysts for future energy storage and conversion systems.

Studies on geochemical characteristics and biomineralization of Cambrian phosphorites, Zhijin, Guizhou Province, China.

Phosphate rocks, an important ore resource in Guizhou Province, China, are mainly hosted within the Sinian Doushantuo Formation and the Cambrian Meishucun Formation. In addition, the phosphate rocks of the Cambrian Meishucun Formation are rich in biological fossils. Although numerous studies investigating the genesis of phosphate deposits have been performed, the relationship between biological activity and the formation of phosphate deposits in the lower Cambrian Meishucun Formation has not been convincingly explained. This study focuses on the biological fossil assemblage, the characteristics of phosphorus, and the relationship between biological and phosphorus enrichment of the lower Cambrian phosphorites. The primary objectives of our study are to analyze the role of organisms in the formation of phosphorites, restore the phosphorus-formation environment of the Cambrian Meishucun Formation, and construct a sedimentary model of the phosphorites in the Meishucun Formation. The results indicate that there is a significant positive correlation between biological activity and the deposition of phosphorites, that is, the higher the degree of biological enrichment and differentiation, the stronger the deposition. The geochemical analysis of several profiles in the Zhijin phosphorite block shows that the phosphorite block was deposited in an oxygen-rich environment and was affected by a high-temperature hydrothermal fluid. Upwelling ocean currents supplied abundant phosphorus and other nutrients, which provided the conditions for small shells and algae to flourish. Biochemical activity was a crucial factor in the deposition of the phosphorite.

Molten-salt-induced phosphorus vacancy defect engineering of heterostructured cobalt phosphides for efficient overall water splitting

A molten salt strategy enables one-step synthesis of heterostructured cobalt phosphides (CoPx) with abundant phosphorus vacancies for efficient overall water splitting.

Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide.

Novel poly(dithiophosphate)s (PDTPs) were successfully synthesized under mild conditions without any additive in the presence of THF or toluene diluents at 60 °C by a direct, catalyst-free reaction between the abundant phosphorus pentasulfide (P4S10) and glycols such as ethylene glycol (EG), 1,6-hexanediol (HD) and poly(ethylene glycol) (PEG). GPC, FTIR, 1H and 31P NMR analyses proved the formation of macromolecules with dithiophosphate coupling groups having P=S and P-SH pendant functionalities. Surprisingly, the ring-opening of THF by the P-SH group and its pendant incorporation as a branching point occur during polymerization. This process is absent with toluene, providing conditions to obtain linear chains. 31P NMR measurements indicate long-time partial hydrolysis and esterification, resulting in the formation of a thiophosphoric acid moiety and branching points. Copolymerization, i.e., using mixtures of EG or HD with PEG, results in polymers with broadly varying viscoelastic properties. TGA shows the lower thermal stability of PDTPs than that of PEG due to the relatively low thermal stability of the P-O-C moieties. The low Tgs of these polymers, from -4 to -50 °C, and a lack of PEG crystallites were found by DSC. This polymerization process and the resulting novel PDTPs enable various new routes for polymer synthesis and application possibilities.

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn's moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydrogen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habitability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean-seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO42-), and total dissolved inorganic P could reach 10-7 to 10-2 mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than <10-10 mol/kg H2O from previous estimates and close to or higher than ∼10-6 mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2O within 105 y, much less than the likely age of Enceladus's ocean (108 to 109 y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability.

Amplified cyanobacterial bloom is derived by polyphosphate accumulation triggered by ultraviolet light

Cyanobacterial blooms appear more strongly, constantly and globally, yet the positive effect of surface solar ultraviolet radiation (UV) on cyanobacterial bloom in natural freshwater habitats is largely ignored. Here in-situ and laboratory studies were jointly designed to probe the mechanism of cyanobacterial bloom promoted by solar UV light. The results showed that solar UV light is a key trigger factor for the accumulation of total phosphorus, dissolved inorganic phosphorus and polyphosphate (polyP) in blooming cyanobacterial cells. The increase of UV dose induces polyP accumulation to result in the excessive phosphorus uptake of blooming cyanobacteria, which provides sufficient phosphorus for cyanobacterial growth in suitable environment. Solar UV light also can promote the contents of phycocyanin, allophycocyanin, and phycoerythrin, producing sufficient ATP by photosynthesis for polyP synthesis in cyanobacterial cells in lake enviroment. The frequent variations of UV irradiance exposure prompts cyanobacteria to absorb excessive phosphorus from suspended solid or sediment. Cyanobacterial intracellular phosphorus is accumulated for their growth. UV light promotes polyP accumulation in blooming cyanobacterial cells to avoid damage. The adsorption amount of phosphorus increases for exuberant growth and then more surface blooming cyanobacteria are exposed to UV light to absorb ample phosphorus. Thus, the positive feedback occurs in lake water bodies with abundant phosphorus. This amplified cycle of cyanobacterial density and phosphorus due to solar UV light in eutrophic water bodies is analogous to a triode to amplify visible photosynthesis by UV light as a base electric current in the energy flow process in lake environment, therefore, “Cyanobacterial Phosphorus Assimilation Ultraviolet Effect” is used to describe this phenomenon. A new explanation is provided for the continuing proliferating mechanism of cyanobacterial bloom. Besides, a new perspective appears on the outbreak of cyanobacterial blooms in natural eutrophic lake water bodies worldwide.

Insight into the formation mechanism of N, P co-doped mesoporous biochar from H3PO4 activation and NH3 modification of biomass

Understanding the formation mechanism of N, P co-doped biochar is critical for preparation of ideal N, P co-doped biochar materials. In this study, N, P co-doped mesoporous biochar was prepared by H3PO4 activation and NH3 modification of biomass. Results showed that, during H3PO4 activation, H3PO4 preferentially reacted with active O-containing groups in biomass. With increase of H3PO4 amount, H3PO4 mainly reacted with carbon fragments. This process removed large amounts of oxygen and carbon of biomass, meanwhile formed lots of vacancies, and then H3PO4 introduced abundant phosphorus (8.95 wt%) and new oxygen into P-doped biochar, accompanying generation of developed mesoporous structure (1089.33 m2/g). P-containing groups introduced were mainly C3-P-O, C-P-O and C-O-P groups. During NH3 modification, NH3 preferentially reacted with PO groups to form amine/amide-N, and then most of them converted into stable pyridinic-N, pyrrolic-N, or NP groups, meanwhile some N-containing groups would further convert into more stable quaternary-N. This process promoted decrease of C3-P-O and C-P-O groups, and formed more PN groups. It introduced abundant nitrogen (12.21 wt%), accompanying generation of more mesopores. At last, possible chemical reaction pathways of H3PO4 activation, and chemical reaction pathways between NH3 and P-containing groups during NH3 modification were proposed for the first time.

RuO2 active particles supported on Ni12P5 as excellent electrocatalysts for Li[sbnd]O2 batteries

Ni12P5 has excellent electrochemical properties due to the existence of a large number of NiP bonds with abundant phosphorus vacancies. RuO2 has good electrical conductivity and catalytic activity, and its OER activity is very significant. In this paper, RuO2 nanoparticles were loaded onto the surfaces of Ni12P5 particles, forming RuO2/Ni12P5/C composite electrode catalytic materials which were prepared and applied to LiO2 cells. The electrochemical tests reveal that the specific capacity of the LiO2 battery with a RuO2/Ni12P5/C electrode reaches 4296 mAh g−1, the cycle life reaches 56 cycles, and the over-potential is effectively controlled at the current density of 200 mA g−1. This improvement is attributable to the effective adsorption of phosphorus vacancies in Ni12P5 and the excellent OER catalytic activity of RuO2. Therefore, this work significantly enhanced the electrochemical performance of the cell, thus laying the foundation for the development of LiO2 batteries.

Structure-regulated Ru particles decorated P-vacancy-rich CoP as a highly active and durable catalyst for NaBH4 hydrolysis

NaBH4 is considered the best hydrogen storage material due to its high hydrogen content of 10.6 wt% and good stability. However, NaBH4 hydrolysis requires an efficient catalyst because of the sluggish reaction kinetics. In this work, we have demonstrated a process of preparing a cobalt phosphide-supported Ru particulate nanocatalyst with abundant phosphorus vacancies for the first time. Electron paramagnetic resonance and transmission electron microscopy revealed that the synthesized Ru9.8/r-CoP catalyst has ample phosphorus vacancies, and Ru species are small particles (~2.5 nm) with uniform dispersion, respectively. More importantly, the optimized Ru9.8/r-CoP catalyst has the lowest activation energy (45.3 kJ mol−1) and exhibits excellent catalytic performance for NaBH4 hydrolysis with a high hydrogen generation rate 9783.3 mLH2 min−1 gcat−1 at 25 °C, which is higher than most of the cobalt-based catalysts. Moreover, the Ru9.8/r-CoP catalyst also shows good reusability. For example, the catalytic performance only declined by ca. 14% after five cycles. The excellent catalytic performance of Ru9.8/r-CoP is attributed to the abundant phosphorus vacancies along with a large specific surface area of r-CoP, which makes the Ru particles smaller and more uniformly dispersed on the surface, thereby exposing more active sites to show improved performance.

Modulating electronic structure of honeycomb-like Ni2P/Ni12P5 heterostructure with phosphorus vacancies for highly efficient lithium-oxygen batteries

Lithium-oxygen batteries (LOBs) have been attracting incremental attention beyond conventional Li-ion batteries owing to their superior theoretical energy density (~3500 Wh kg−1). Developing gas diffusion electrodes with high catalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is considered as one of the most promising strategies to promote the practical application of this novel system. Herein, a honeycomb-like Ni2P/Ni12P5 heterostructure with abundant phosphorus vacancies in situ growing on Ni foam (Ni2P/Ni12P5@NF) is developed as an effective and stable electrode for LOBs. Phosphorus vacancies are capable of inducing delocalization of constrained electrons near the Ni-P bonds, thereby regulating the band gap to enhance both the conductivity and the catalytic activity for oxygen electrode reactions. In addition, the modulation of electronic structure along the heterogeneous interface between Ni12P5 and Ni2P optimizes the adsorption of oxygenated intermediates, which is beneficial to accelerate the interface reaction kinetics of oxygen electrode reactions. Impressively, the LOBs with Ni2P/Ni12P5@NF containing abundant phosphorus vacancies exhibit low overpotential of 0.89 V, ultra-high discharge specific capacity of 13254.1 mA h g−1, and remarkable durability of over 500 h. This work concerning engineering heterostructure with rich vacancies can provide new guidance for the development of high performance electrocatalysts.