Effective Energy Storage Performance Derived from 3D Porous Dendrimer Architecture Metal Phosphides//Metal Nitride-Sulfides.

The present work addresses the limitations by fabricating a wide range of negative electrodes, including metal nitrides/sulfides on a 3D bimetallic conductive porous network (3D-Ni and 3D-NiCo) via a dynamic hydrogen bubble template (DHBT) method followed by vapour phase growth (VPG) process. Among the prepared negative electrodes, the 3D-Fe3S4-Fe4N/NiCo nanostructure demonstrates an impressive specific capacitance (Cs) of 1125 F g-1 (2475 mF cm-2) at 1 A g-1 with 80% capacitance retention over 5000 cycles. Similarly, a 3D-Mn3P nanostructured positive electrode fabricated via electrodeposition followed by a phosphorization process exhibits a maximum specific capacity (Cg) of 923.04 C g-1 (1846.08 mF cm-2) at 1 A g-1 with 80% stability. A 3D-Mn3P/Ni//3D-Fe3S4-Fe4N/NiCo supercapattery is also assembled, and it shows a notable CS of 151 F g-1 at 1 A g-1, as well as a high energy density (ED) of 51 Wh kg-1,a power density (PD) of 782.57 W kg-1 and a capacitance efficiency of 76% over 10 000 cycles. This may be ascribed to the use of a bimetallic 3D porous conductive template and the attachment of transition metal sulfide and nitride. The development of negative electrodes and supercapattery devices is greatly aided by this exploration of novel synthesis techniques and material choice.

Magnetic Nanoparticles with Fe-N and Fe-C Cores and Carbon Shells Synthesized at High Pressures.

Nanoparticles of iron carbides and nitrides enclosed in graphite shells were obtained at 2 ÷ 8 GPa pressures and temperatures of around 800 °C from ferrocene and ferrocene-melamine mixture. The average core-shell particle size was below 60 nm. The graphite-like shells over the iron nitride cores were built of concentric graphene layers packed in a rhombohedral shape. It was found that at a pressure of 4 GPa and temperature of 800 °C, the stability of the nanoscale phases increases in a Fe7C3 > Fe3C > Fe3N1+x sequence and at 8 GPa in a Fe3C > Fe7C3 > Fe3N1+x sequence. At pressures of 2 ÷ 8 GPa and temperatures up to 1600 °C, iron nitride Fe3N1+x is more stable than iron carbides. At 8 GPa and 1600 °C, the average particle size of iron nitride increased to 0.5 ÷ 1 µm, while simultaneously formed free carbon particles had the shape of graphite discs with a size of 1 ÷ 2 µm. Structural refinement of the iron nitride using the Rietveld method gave the best result for the space group P6322. The refined composition of the samples obtained from a mixture of ferrocene and melamine at 8 GPa/800 °C corresponded to Fe3N1.208, and at 8 GPa/1650 °C to Fe3N1.259. The iron nitride core-shell nanoparticles exhibited magnetic behavior. Specific magnetization at 7.5 kOe of pure Fe3N1.208 was estimated to be 70 emu/g. Compared to other methods, the high-pressure method allows easy synthesis of the iron nitride cores inside pure carbon shells and control of the particle size. And in general, pressure is a good tool for modifying the phase and chemical composition of the iron-containing cores.

Ferrous disulfide and iron nitride sites on hydrochar to enhance synergistic adsorption and reduction of hexavalent chromium.

In this study, a novel hydrochar containing ferrous disulfide (FeS2) and iron nitride (FeN) was prepared via a one-pot hydrothermal method to enhance the synergistic adsorption and reduction of hexavalent chromium (Cr(VI)). This material (Fe3-SNHC) exhibited a Cr(VI) removal capacity of 431.3 mg·g-1 and high tolerance to coexisting anions at pH 2. Adsorption occurred via monolayer chemisorption. Variation in material structure and density functional theory calculations proved that multiple active sites formed by interactions between heteroatoms improved the chemical inertness of hydrochar. FeN and FeS2 with two electron-donating groups had strong reducing ability to facilitate the conversion of Cr(VI) to trivalent chromium. It was concluded that next to electrostatic adsorption and complexation, synergistic reduction among multiple active sites were the dominant mechanisms involved in the removal Cr(VI). This study shows that Fe3-SNHC is a promising and environment-friendly material for Cr(VI) to remove it from wastewater.

Domain Matching Strategy for Orientation Control of van der Waals Epitaxial Perovskite Thin Films.

The advantages of van der Waals epitaxy have attracted great interest because they can meet the requirements that conventional epitaxy struggles to satisfy. The weak adatom-substrate interaction without directional covalent bonding drastically relaxes the lattice matching limitation. However, the weak adatom-substrate interaction also leads to ineffectiveness in directing the crystal growth structure, limiting it to one orientation in epitaxial growth. In this work, we propose a domain matching strategy to guide the perovskite-type crystal epitaxial growth on 2D substrates, and we have demonstrated selective deposition of highly (001)-, (110)-, and (111)-oriented epitaxial Fe4N thin films on mica substrates using applicable transition structure design. Our work makes it possible to achieve and control different orientations of van der Waals epitaxy on the same substrate.

Iron nitride nanoparticles for rapid dechlorination of mixed chlorinated ethene contamination.

Sulfidation and, more recently, nitriding have been recognized as promising modifications to enhance the selectivity of nanoscale zero-valent iron (nZVI) particles for trichloroethene (TCE). Herein, we investigated the performance of iron nitride (FexN) nanoparticles in the removal of a broader range of chlorinated ethenes (CEs), including tetrachloroethene (PCE), cis-1,2-dichloroethene (cis-DCE), and their mixture with TCE, and compared it to the performance of sulfidated nZVI (S-nZVI) prepared from the same precursor nZVI. Two distinct types of iron nitride (FexN) nanoparticles, containing γ'-Fe4N and ε-Fe2-3N phases, exhibited substantially higher PCE and cis-DCE dechlorination rates compared to S-nZVI. A similar effect was observed with a CE mixture, which was completely dechlorinated by both types of FexN nanoparticles within 10 days, whereas S-nZVI was able to remove only about half of the amount, most of which being TCE. Density functional theory calculations further revealed that the cleavage of the first C-Cl bond was the rate-limiting step for all CEs dechlorinated on the γ'-Fe4N(001) surface, with the reaction barriers of PCE and cis-DCE being 29.9, and 40.8 kJ mol-1, respectively. FexN nanoparticles proved to be highly effective in the remediation of PCE, cis-DCE, and mixed CE contamination.

Characterization of a Proposed Terminal Iron(III) Nitride Intermediate of Nitrogen Fixation Stabilized by a Trisphosphine-Borane Ligand.

Terminal iron nitrides (Fe≡N) have been proposed as intermediates of Fe-mediated nitrogen fixation, and well-defined synthetic iron nitrides have been characterized in high oxidation states, including FeIV , FeV , and FeVI . This study reports the generation and low temperature characterization of a terminally bound iron(III) nitride, P3 B Fe(N) (P3 B =tris(o-diisopropylphosphinophenyl)borane), which is a proposed intermediate of iron-mediated nitrogen fixation by the P3 B Fe-catalyst system. CW- and pulse EPR spectroscopy (HYSCORE and ENDOR), supported by DFT calculations, help to define a 2 A ground state electronic structure of this C3 -symmetric nitride species, placing the unpaired spin in a sigma orbital along the B-Fe-N vector; this electronic structure is distinct for an iron nitride. The unusual d5 -configuration is stabilized by significant delocalization (≈50 %) of the unpaired electron onto the axial boron and nitrogen ligands, with a majority of the spin residing on boron.

Coordination compound-derived Fe4N/Fe3N/Fe/CNT for efficient electrocatalytic oxygen evolution: a facile one-step synthesis in the absence of extra nitrogen source.

By annealing an Fe(III)-coordination compound (Fe-CC), [FeCl3(Hbta)2] (Hbta = benzotriazole) in the presence of a carbon nanotube precursor (PCNT) template, an Fe4N/Fe3N/Fe/CNT heterostructure was successfully synthesized without an extra nitrogen source. The decomposition of the Hbta in Fe-CC under high-temperature annealing can produce carbon sheets and reduced graphene oxide (rGO), and the presence of CNTs can alleviate the stacking of thein situ-generated carbon materials. Meanwhile, iron nitride nanoparticles (NPs) can be anchored on the carbon sheets, and the anchoring effect efficiently prevents the agglomeration of NPs and increases the amount of active catalytic sites for the oxygen evolution reaction (OER). Fe4N/Fe3N/Fe/CNT shows an excellent OER activity with a Tafel slope of 63 mV dec-1as well as overpotentials of 121 (η10) and 275 mV (η100) at 10 and 100 mA cm-2, respectively - far exceeding commercial RuO2and other catalysts. Density functional theory calculations show that the excellent OER performance of Fe4N/Fe3N/Fe/CNT is associated with the Fe4N/Fe3N heterojunction, which can improve the electron conductivity and boost the electron transfer from N to Fe. The Fe4N/Fe3N/Fe/CNT catalyst exhibits long-term OER activity during 100 h of electrolysis at 20 mA cm-2. This is related to the dual coatings of thein situ-generated thin carbon shell and few-layered rGO on the surface of the iron nitride NPs, which can protect the fast leaching of iron nitride during the OER process. Furthermore, the effects of the annealing temperature, the PCNT template and the heating rate on the calcined products were investigated.

Poly(ionic liquid) Nanovesicle-Templated Carbon Nanocapsules Functionalized with Uniform Iron Nitride Nanoparticles as Catalytic Sulfur Host for Li-S Batteries.

Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazolium-based PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C"). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g-1 at 0.5 C initially, and a remaining value of 930 mAh g-1 after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g-1 at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion.

The nanotoxicity assessment of cube-like iron nitride magnetic nanoparticles at the organismal level of nematode Caenorhabditis elegans.

Magnetic nanoparticles (NPs) are suitable candidates for various medical and biological applications, despite some concerns that they may have negative impacts on human health. In this study, the toxicity effects of magnetic NPs consisting of α"-Fe16N2 captured and bioaccumulated by the nematode Caenorhabditis elegans (C. elegans) in the early larval stage are evaluated. The choice of α"-Fe16N2 NPs is based on their good structural stability when stored in saline solution and high magnetic performance. The uptake and bioaccumulation of α"-Fe16N2 NPs in intestinal cells of C. elegans was evidenced by transmission electron microscopy. After exposure to NPs up to 40 mg mL-1, C. elegans larval development, survival, feeding behavior, defecation cycles, movement and reproduction were monitored. C. elegans survival and other monitored behavioral evolutions do not show significant changes, except for a slight statistical reduction in the reproductive profile. Therefore, the present results are promising and very encouraging for investigations of applications of α"-Fe16N2 NPs in the biomedical area.

Iron Nitride Nanoparticles for Enhanced Reductive Dechlorination of Trichloroethylene.

Nitriding has been used for decades to improve the corrosion resistance of iron and steel materials. Moreover, iron nitrides (FexN) have been shown to give an outstanding catalytic performance in a wide range of applications. We demonstrate that nitriding also substantially enhances the reactivity of zerovalent iron nanoparticles (nZVI) used for groundwater remediation, alongside reducing particle corrosion. Two different types of FexN nanoparticles were synthesized by passing gaseous NH3/N2 mixtures over pristine nZVI at elevated temperatures. The resulting particles were composed mostly of face-centered cubic (γ'-Fe4N) and hexagonal close-packed (ε-Fe2-3N) arrangements. Nitriding was found to increase the particles' water contact angle and surface availability of iron in reduced forms. The two types of FexN nanoparticles showed a 20- and 5-fold increase in the trichloroethylene (TCE) dechlorination rate, compared to pristine nZVI, and about a 3-fold reduction in the hydrogen evolution rate. This was related to a low energy barrier of 27.0 kJ mol-1 for the first dechlorination step of TCE on the γ'-Fe4N(001) surface, as revealed by density functional theory calculations with an implicit solvation model. TCE dechlorination experiments with aged particles showed that the γ'-Fe4N nanoparticles retained high reactivity even after three months of aging. This combined theoretical-experimental study shows that FexN nanoparticles represent a new and potentially important tool for TCE dechlorination.

A Facile Route for the Preparation of Monodisperse Iron nitride at Silica Core/shell Nanostructures.

Uniform-sized iron oxide nanoparticles obtained from the solution phase thermal decomposition of the iron-oleate complex were encapsulated inside the silica shell by the reverse microemulsion technique, and then thermal treatment under NH3 to transfer the iron oxide to iron nitride. The transmission electron microscopy images distinctly demonstrated that the as-prepared iron nitride at silica core/shell nanostructures were highly uniform in particle-size distribution. By using iron oxide nanoparticles of 6.1, 10.3, 16.2, and 21.8 nm as starting materials, iron nitride nanoparticles with average diameters of 5.6, 9.3, 11.6, and 16.7 nm were produced, respectively. The acid-resistant properties of the iron nitride at silica core/shell nanostructures were found to be much higher than the starting iron oxide at silica. A superconducting quantum interference device was used for the magnetic characterization of the nanostructure. Besides, magnetic resonance imaging (MRI) studies using iron nitride at silica nanocomposites as contrast agents demonstrated T 2 enhanced effects that were dependent on the concentration. These core/shell nanostructures have enormous potential in magnetic nanodevice and biomedical applications. The current process is expected to be easy for large-scale and transfer other metal oxide nanoparticles.

Phase Stability of Iron Nitride Fe4N at High Pressure-Pressure-Dependent Evolution of Phase Equilibria in the Fe-N System.

Although the general instability of the iron nitride γ'-Fe4N with respect to other phases at high pressure is well established, the actual type of phase transitions and equilibrium conditions of their occurrence are, as of yet, poorly investigated. In the present study, samples of γ'-Fe4N and mixtures of α Fe and γ'-Fe4N powders have been heat-treated at temperatures between 250 and 1000 °C and pressures between 2 and 8 GPa in a multi-anvil press, in order to investigate phase equilibria involving the γ' phase. Samples heat-treated at high-pressure conditions, were quenched, subsequently decompressed, and then analysed ex situ. Microstructure analysis is used to derive implications on the phase transformations during the heat treatments. Further, it is confirmed that the Fe-N phases in the target composition range are quenchable. Thus, phase proportions and chemical composition of the phases, determined from ex situ X-ray diffraction data, allowed conclusions about the phase equilibria at high-pressure conditions. Further, evidence for the low-temperature eutectoid decomposition γ'→α+ε' is presented for the first time. From the observed equilibria, a P-T projection of the univariant equilibria in the Fe-rich portion of the Fe-N system is derived, which features a quadruple point at 5 GPa and 375 °C, above which γ'-Fe4N is thermodynamically unstable. The experimental work is supplemented by ab initio calculations in order to discuss the relative phase stability and energy landscape in the Fe-N system, from the ground state to conditions accessible in the multi-anvil experiments. It is concluded that γ'-Fe4N, which is unstable with respect to other phases at 0 K (at any pressure), has to be entropically stabilised in order to occur as stable phase in the system. In view of the frequently reported metastable retention of the γ' phase during room temperature compression experiments, energetic and kinetic aspects of the polymorphic transition γ'⇌ε' are discussed.

Cytotoxicity evaluation of iron nitride nanoparticles for biomedical applications.

Magnetic nanoparticles are widely studied for their use in various therapeutic and diagnostic purposes. As biomaterials, their biocompatibility is as important as their magnetic properties. Iron nitride (Fex Ny ) has excellent magnetic properties, and thus Fex Ny nanoparticles could be useful as potential biomaterials. However, the biocompatibility of Fex Ny nanoparticles is yet to be investigated. In this study, we assessed the biocompatibility of Fex Ny nanoparticles by evaluating their direct-contact cytotoxicity compared with that of magnetite nanoparticles (MNPs). Rat fibroblasts were incubated with the nanoparticle samples dispersed in culture medium at concentrations of 10, 50, and 100 µg/ml. The DNA concentration measurement, MTT assay, and trypan blue exclusion test were conducted after days 1 and 3 of incubation. After day 1, the cell viability decreased, and cell death increased with increasing sample concentration when compared with the control. However, after day 3, there were no significant differences when compared with the control, irrespective of the sample concentrations. Further, there were no significant differences between the Fex Ny nanoparticles and MNPs at the same concentrations in all the cytotoxicity evaluation tests. Therefore, it is suggested that Fex Ny nanoparticles might be as cytocompatible as the conventional MNPs.

Subatomic Distortion of Surface Monolayer Lattice Visualized by Moiré Pattern.

Mapping of the local lattice distortion is required to understand the details of the chemical and physical properties of thin films. However, the resolution by the direct microscopic methods was insufficient to detect the local distortion. Here, we have demonstrated that the local distortion of a monatomic film on a substrate is estimated with high resolution using the moiré pattern of the topographic scanning tunneling microscopy image. The analysis focused on the apparently low centers of the moiré pattern of the hexagonal iron nitride monolayer on the Cu(111) substrate. The local distortion was visualized by estimating the displacement of the experimentally detected center position from the ideal position that is extracted from the adjacent center positions. The map of the local distortion revealed that the subsurface impurities are preferentially located on the largely distorted areas. This approach is widely applicable to other thin films on the substrates.

Iron Nitride@C Nanocubes Inside Core-Shell Fibers to Realize High Air-Stability, Ultralong Life, and Superior Lithium/Sodium Storages.

Poor air stability and severe structure pulverization are crucial issues for metal nitrides in metal-ion batteries. Herein, core-shell hybrid fibers (CSHN fiber) filled with metal nitride@C hollow nanocubes are introduced to be a new self-supporting anode for sodium-ion and lithium-ion batteries. The hierarchical carbon network provides fast electronic pathways and gives high protection for iron nitrides. Meanwhile, the self-supporting electrode avoids the complicated electrode fabrication process and decreases the opportunity to air exposure. Moreover, its porous nature ensures high buffer to volumetric expansion and improves the cycling stability. Therefore, it is a good platform to realize fast kinetics and high durability. For the first time, Fe2N@N-doped carbon CSHN hybrid fibers are constructed. Their influences on air stability and electrochemical behaviors are studied. Impressively, they achieve high stabilities in both lithium-ion (92.8%, at 5 A g-1, 1000 cycles) and sodium-ion (95.6%, at 2 A g-1, 2000 cycles) batteries. Therefore, this work introduces a new method to construct superior performance nitride anodes. Moreover, it also provides a new insight on the fabrication of highly efficient structures for diverse functional materials.

Defect-Rich FeN0.023/Mo2C Heterostructure as a Highly Efficient Bifunctional Catalyst for Overall Water-Splitting.

The innovation in highly efficient, stable, and economical bifunctional overall water-splitting electrocatalysts is critical in developing sustainable energy, but it remains challenging. In this research, we have developed an unsophisticated method to synthesize hybrid nanoparticles (FeN0.023/Mo2C/C) uniformly dispersed in nitrogen-doped carbon nanosheets. The two active components FeN0.023 and Mo2C are coupled to form an FeN0.023/Mo2C/C heterostructure being a highly efficient electrocatalyst, which gives low overpotentials of 227/76 mV for OER/HER at 10 mA cm-2 current density. The alkaline-electrolyzer with FeN0.023/Mo2C/C as the anode-cathode catalyst needs merely 1.55 V to reach 10 mA cm-2 and can maintain a stable state for a minimum of 10 h. This research gives a simple effective resolution in designing affordable and useful overall water-splitting electrocatalysts.

Phosphorus-Doped Iron Nitride Nanoparticles Encapsulated by Nitrogen-Doped Carbon Nanosheets on Iron Foam In Situ Derived from Saccharomycetes Cerevisiae for Electrocatalytic Overall Water Splitting.

It is vitally essential to propose a novel, economical, and safe preparation method to design highly efficient electrocatalysts. Herein, phosphorus-doped iron nitride nanoparticles encapsulated by nitrogen-doped carbon nanosheets are grown directly on the iron foam substrate (P-Fe3 N@NC NSs/IF) by in situ deriving from Saccharomycetes cerevisiae (S. cerevisiae), where anion elements of C, N, and P all from S. cerevisiae replace the hazardous CH4 , NH3 , and H3 P. The diffusion pattern of N, P in S. cerevisiae and contact form between metal and S. cerevisiae observably affect the composition and phase of the product during high-temperature calcination. The obtained P-Fe3 N@NC NSs/IF demonstrates superior electrocatalytic performance for the hydrogen evolution reaction and oxygen evolution reaction, also satisfying durability. Theoretical calculation confirms that Fe sites of P-Fe3 N serve as the active center, and N sites and P doping regulate the hydrogen binding strength to enhance catalytic ability. Additionally, the two-electrode electrolyzer assembled by P-Fe3 N@NC NSs/IF as both anode and cathode electrodes needs only 1.61 V to reach 10 mA cm-2 for overall water splitting with a superb stability. The S. cerevisiae-based process presents a feasible approach for synthesis of nitrides, carbides, phosphides, and electrocatalytic applications.

Ferromagnetic ε-Fe2MnN: High-Pressure Synthesis, Hardness and Magnetic Properties.

The iron manganese nitride Fe2MnN was obtained by high-pressure-high-temperature synthesis from ζ-Fe2N and elemental Mn at 15(2) GPa and 1573(200) K. The phase crystallizes isostructural to binary ε-Fe3N. In comparison to the corresponding binary iron nitride, the microhardness of ε-Fe2MnN is reduced to 6.2(2) GPa. Above about 800 K the ternary compound decomposes exothermally under loss of nitrogen. ε-Fe2MnN is ferromagnetic with a Curie temperature of roughly 402 K.

Bio-Derived Hierarchical Multicore-Shell Fe2N-Nanoparticle-Impregnated N-Doped Carbon Nanofiber Bundles: A Host Material for Lithium-/Potassium-Ion Storage.

Despite the significant progress in the fabrication of advanced electrode materials, complex control strategies and tedious processing are often involved for most targeted materials to tailor their compositions, morphologies, and chemistries. Inspired by the unique geometric structures of natural biomacromolecules together with their high affinities for metal species, we propose the use of skin collagen fibers for the template crafting of a novel multicore-shell Fe2N-carbon framework anode configuration, composed of hierarchical N-doped carbon nanofiber bundles firmly embedded with Fe2N nanoparticles (Fe2N@N-CFBs). In the resultant heterostructure, the Fe2N nanoparticles firmly confined inside the carbon shells are spatially isolated but electronically well connected by the long-range carbon nanofiber framework. This not only provides direct and continuous conductive pathways to facilitate electron/ion transport, but also helps cushion the volume expansion of the encapsulated Fe2N to preserve the electrode microstructure. Considering its unique structural characteristics, Fe2N@N-CFBs as an advanced anode material exhibits remarkable electrochemical performances for lithium- and potassium-ion batteries. Moreover, this bio-derived structural strategy can pave the way for novel low-cost and high-efficiency syntheses of metal-nitride/carbon nanofiber heterostructures for potential applications in energy-related fields and beyond.

High-Efficient, Stable Electrocatalytic Hydrogen Evolution in Acid Media by Amorphous Fex P Coating Fe2 N Supported on Reduced Graphene Oxide.

Development of efficient and durable non-Pt catalysts for hydrogen evolution reaction (HER) in acid media is highly desirable. Iron nitride has emerged as a promising catalyst for its cost-effective nature, but the corresponding acidic stability must be promoted. Herein, phosphorus-decorated Fe2 N and reduced graphene oxide (P-Fe2 N/rGO) composite are designed and synthesized. X-ray photoelectron spectroscopy and X-ray absorption fine structure (XAFS) show that a thin layer amorphous iron phosphide is coated on the surface of Fe2 N nanoparticles, which could be responsible for the well resistance of chemical corrosion in acidic media. Meanwhile, the P-decoration could tune the electronic state and coordination environment of iron atom as evidenced by XAFS, resulting in dramatically enhanced electrocatalytic activity of P-Fe2 N/rGO. Density functional theory calculations reveal that both the P-connected N atoms and the Fe atoms in P-Fe2 N/rGO catalyst are the main active sites for H* adsorption. The hydrogen-binding free energy |ΔGH* | value is close to zero for P-Fe2 N/rGO, suggesting a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, P-Fe2 N/rGO catalyst could achieve a low ηonset of 22.4 mV, a small Tafel plot of 48.7 mV dec-1 , and remarkable stability for HER in acid electrolyte.