Electrodeposited NiMoP catalysts on carbon felt for hydrogenation of indigo during electrocatalytically splitting water

Electrochemical hydrogenation is an environmentally favorable alternative to chemical reduction of indigo because it performs under ambient conditions using water as the donor of hydrogen. The purpose of this work is to fabricate electrocatalysts with high activity and durability for electrocatalytic hydrogenation of indigo. This work compares the performances of a series of Ni based catalysts (Ni, NiMo, NiP and NiMoP) on the substrate of carbon felt (CF) for electrolyzing water. Both the overpotential and Tafel slop are decreased as a function of the components as Ni > NiMo > NiP > NiMoP. Hence, NiMoP/CF shows the excellent performance based on the thermodynamics (η₁₀ = 239 mV) and kinetics (Tafel slope = 89.7 mV·dec^?1) for splitting water. Further, the electrode of NiMoP/CF was used for the electrocatalytic hydrogenation of indigo. The conversion efficiency and Faradic efficiency can be improved as 26.2% and 10.7% respectively. Furthermore, the dyeing behavior of the electrohydrogenated indigo is similar to that of conventional reduction methods. Thus, the present work offers foundational results and paves the way for the design of new catalytic materials for the reduction of vat dyes.     

Application of a deep eutectic solvent to prepare nanocrystalline Ni and Ni/TiO2 coatings as electrocatalysts for the hydrogen evolution reaction

The paper reports the electrochemical deposition of nanocrystalline nickel and composite nickel-titania films as effective electrocatalysts for the hydrogen evolution reaction. To produce the composite Ni/TiO₂ electrodeposits, a plating bath based on a deep eutectic solvent, a novel kind of ionic liquids, was used for the first time. The electrolyte contained ethaline (a eutectic mixture of choline chloride and ethylene glycol), 1 M NiCl₂⋅6H₂O and the addition of extra water (3, 6, 9 mol dm⁻³). Titania dispersed phase was introduced into the electrolyte as nanopowder Degussa P 25 (0–10 g dm⁻³). It was shown that the introduction of extra water to the plating bath allowed appreciably increasing the content of TiO₂ phase in the coating (from ca. 2 to 10 wt%). The effects of electrolysis conditions on the TiO₂ content in the coatings, surface morphology and microstructure were determined. The results of voltammetry measurements showed that the Ni and composite Ni/TiO₂ coatings electrodeposited from the plating electrolyte based on a deep eutectic solvent exhibit improved electrocatalytic properties towards the hydrogen evolution reaction as compared with deposits obtained from commonly used aqueous electrolytes. The mechanism of the hydrogen evolution reaction on the Ni and composite Ni/TiO₂ coatings is a combination of Volmer-Heyrovsky reactions. The introduction of TiO₂ particles into the nickel matrix results in the acceleration of the hydrogen evolution reaction. An improved catalytic activity of Ni/TiO₂ composites towards the hydrogen evolution reaction can be associated with the presence of titanium-containing redox couples on the surface.     

Remarkable electrocatalytic activity of Ni-nanoparticles on MOF-derived ZrO2-porous carbon/reduced graphene oxide towards methanol oxidation

In the present work, a porous carbonaceous platform containing zirconium oxide was used for spreading Ni nanoparticles, and applied to methanol oxidation. The platform was obtained by calcination of a metal-organic framework (MOF) attached to graphene oxide. Nickel nanoparticles were then deposited on the nanocomposite by chemical reduction from a Ni²⁺ solution. The obtained electrocatalyst was characterized by different methods. An excellent electrocatalytic behavior was observed towards methanol oxidation in alkaline medium (j ~ 240 mA cm^?2 or ~ 626 mA mg^?1 in 1.0 M methanol). The results of methanol oxidation by various electrochemical studies (cyclic voltammetry, electrochemical impedance spectroscopy, chronoamperometry and chronopotentiometry) revealed the effective synergy between reduced graphene oxide, porous carbon material, ZrO₂ metal oxide and Ni nanoparticles. Good durability and stability of the proposed electrocatalyst and significantly increased current density of methanol oxidation suggest it as a potential alternative for Pt-based electrocatalysts in direct methanol fuel cells.     

Electrocatalytic activity of nanostructured Ni and Pd–Ni on Vulcan XC-72R carbon black for methanol oxidation in alkaline medium

Ni and Pd–Ni nanoparticles were chemically deposited on Vulcan XC-72R carbon black by impregnation method using NaBH₄ as a reducing agent. The prepared electrocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). The electrocatalytic activity of Ni/C and Pd–Ni/C electrocatalysts towards methanol oxidation in 0.5 M KOH solution was examined using cyclic voltammetry and chronoamperometry. Two methanol oxidation peaks were observed on the Pd–Ni/C at 0 and +860 mV. Their current density values are higher than those at Pd/C and Ni/C electrocatalysts by 1.92 and 1.68 times, respectively. The catalytic rate constant of methanol oxidation reaction at Ni/C and Pd–Ni/C electrocatalysts in (0.2 M MeOH + 0.5 M KOH) solution was estimated using double-step chronoamperometry as 5.64 × 10³ and 6.25 × 10³ cm³ mol⁻¹ s⁻¹, respectively. Pd–Ni/C is more stable than Pd/C and Ni/C electrocatalysts. Therefore, Pd–Ni/C is a suitable as a less expensive electrocatalyst for methanol oxidation in alkaline medium.     

Design and synthesis of Pd decorated rGO-MoSe2 2D hybrid network as high performance electrocatalyst toward methanol electrooxidation

Direct methanol fuel cells (DMFCs) have attracted profound interest for development of future green energy sources, which are being powered by methanol as a fuel. The critical problem identified with DMFCs is the deactivation of electrocatalysts resulting from the adsorption of CO during methanol oxidation. In this work, we have employed a new synthetic approach by a green microwave method for the synthesis of hybrid Pd-MoSe₂-rGO and Pd-rGO nanocomposites. The synthesized electrocatalysts were successfully characterized by XRD, which is used to identify the crystalline phases, FESEM and TEM analyses for morphological features, XPS for analyzing the elements constituting the composites surface and Raman spectroscopy for the analysis of molecular structural bonding. Electrocatalytic activity was explored by cyclic voltammetry (CV), chronoamperometry (CA) and CO stripping techniques. Electroactive surface area (EASA) of the developed hybrid electrocatalyst Pd-MoSe₂-rGO (51.81 m² g⁻¹_Pd) was more than 3.4 times superior activity than that of Pd-rGO catalyst (15.30 m² g⁻¹_Pd). It was observed that the synthesized catalyst with 3D cross-linked hybrid network facilitated even distribution of metal nanoparticles and exhibited nearly four times enhanced electrocatalytic activity (1935 mA mg⁻¹_Pd) towards methanol oxidation reaction (MOR) in alkaline medium, compared to Pd-rGO (546 mA mg⁻¹_Pd). Under constant applied potential investigations, catalytic activity of Pd-MoSe₂-rGO was nearly 50 times higher than that of Pd-rGO at the end of about 1 h. The ease of the availability of more active sites and high tolerance against CO poisoning resulted by the insertion of MoSe₂ led to enhanced catalytic activity of Pd-MoSe₂-rGO towards MOR. It is conceived that this synthetic strategy by employing a combination of 2D materials like MoSe₂, graphene and Pd nanoparticles together as building blocks for 3D hybrid network led to efficient electrocatalysts with high surface area and long-term stability towards methanol oxidation. This synthetic strategy exhibits a promising prospect to develop durable and stable electrocatalyst for DMFC applications.     

Tuning of electrocatalytic activity of mixed metal dichalcogenides supported NiMoP coatings for alkaline hydrogen evolution reaction

The mixed metal dichalcogenides combination of WS₂–MoS₂ was coated onto Cu substrate by electroless NiMoP plating technique and the electrocatalytic hydrogen evolution reaction (HER) performance was investigated. The enhanced structural, morphological parameters and boosted electrocatalytic performance of the various metal-metal molar ratio of WS₂–MoS₂ onto NiMoP plate were identified under variable operating conditions and it was successfully evaluated by various characterization techniques. The well-defined crystalline nature, phase, particle size, structure, elemental analysis and surface morphology of prepared coatings were analyzed by FESEM, XRD, AFM and EDS mapping. The electrochemical analysis was performed using open circuit potential (OCP) analysis, chronoamperometry (CA), electrochemical impedance spectroscopy (EIS), Tafel curves, linear sweep voltammetry (LSV), cyclic voltammetry (CV) and polarization studies to find the activity of prepared electrocatalyst towards electrochemical hydrogen evolution reactions. The performance of bare NiMoP and WS₂–MoS₂/NiMoP plates were compared and found that the HER activity of NiMoP can be reinforced by composite incorporation through the synergic effect arises with in the catalytic system, which improves surface roughness and enhances the magnitude of electrocatalyst toward HER. The achievement of enhanced catalytic performance of coatings was authenticate by the kinetic parameters such as decreases in Tafel slope (98 mV dec^?1), enhanced exchange current densities (9.32 × 10^?4 A cm^?2), and a lower overpotential. The consistent performance and durability of the catalyst were also investigated. The enhanced electrocatalytic activity of WS₂–MoS₂/NiMoP coatings increased with respect to the surface-active sites associated with combination of mixed dichalcogenides and the synergic effect arises in between different components present in the coating system. This work envisages the progressive strategies for the economical exploration of a novel WS₂–MoS₂/NiMoP water splitting catalyst used for large scale H₂ generation. The prepared WS₂–MoS₂/NiMoP embedded Cu substrate possess high catalytic activity due to its least overpotential of 101 mV at a benchmark current density of 10 mA cm^?2, which demonstrated the sustainable, efficient and promising electrocatalytic property of prepared catalyst towards HER under alkaline conditions.     

NiMo/Cu-nanosheets/Ni-foam composite as a high performance electrocatalyst for hydrogen evolution over a wide pH range

We designed and fabricated non-precious and highly efficient electrocatalysts of nickelmolybdenum/copper-nanosheets/nickel-foam composites (NiMo/Cu-NS/NF) by step electrodepositions, combining with chemical oxidation method. The catalysts were charaterized by means of SEM, XRD and XPS spectra. Their electrocatalytic activities were assessed by hydrogen evolution reactions (HER) over a wide pH range, where acidic, neutral and alkaline electrolytes were used, respectively. Benefiting from the unique midlayer Cu nanosheets (NS) architecture and optimum Mo–Ni composition at the surface layer which led to high electronic conductivity and large electrochemically active surface area (ECSA), the NiMo/Cu-NS/NF-2 catalyst displayed superior electrocatalytic activities with low overpotentials of η₁₀ = 43, 86 and 89 mV in 0.5 M H₂SO₄, 1.0 M PBS and 1.0 M KOH electrolyte, respectively. Especially in the acidic condition, it exhibited the best electrocatalytic activity with smaller Tafel slope of 54 mV dec^?1 and higher exchange current density of 1.93 mA cm^?2.     

Zn-substituted MnCo2O4 nanostructure anchored over rGO for boosting the electrocatalytic performance towards methanol oxidation and oxygen evolution reaction (OER)

Mixed valence spinel oxides have emerged as an attractive and inexpensive anode electrocatalyst for water oxidation to replace noble metals based electrocatalysts. The present work demonstrates the facile synthesis of Zn substituted MnCo₂O₄ supported on 3D graphene prepared by simple hydrothermal technique and its application as an electrocatalyst for water oxidation and methanol oxidation. The physico-chemical properties of the nanocatalyst were studied using various microscopic, spectroscopic and diffraction analyses confirming the formation of the composite. The electrocatalytic performance of the prepared electrocatalyst was evaluated using potentiodynamic, potentiostatic and impedance techniques. The synthesized Zn_1-xMn_xCo₂O₄/rGO electrocatalyst with x = 0.2 and 0.4 offered the same onset potential and overpotential at 10 mA/cm². However, catalyst x = 0.4 delivered a higher current density indicating the superiority of the same over other compositions which is attributed to better kinetics that it possessed for OER as revealed by the smallest Tafel slope (80.6 mV dec⁻¹). The prepared electrocatalysts were tested for methanol oxidation in which electrocatalyst Zn_1-xMn_xCo₂O₄/rGO with x = 0.4 shows a better electrochemical performance in oxidizing methanol with the higher current density of 142.3 mA/cm². The above catalyst also revealed excellent stability and durability during both MOR and OER, suggesting that it can be utilized in practical applications.     

Interfacial interaction between NiMoP and NiFe-LDH to regulate the electronic structure toward high-efficiency electrocatalytic oxygen evolution reaction

Development of low-cost, high-efficiency electrocatalysts for the oxygen evolution reaction (OER) is challenging, even though it is critical for the overall electrochemical splitting. Herein, we report a NiMoP@NiFe-LDH heterostructure electrode supported on nickel foam. The study shows that the electrocatalytic activity for the OER can be improved by coupling NiMoP and NiFe-LDH. The resulting NiMoP@NiFe-LDH heterostructure exhibited remarkable catalytic performance with an ultralow overpotential of only 299 mV at a current density of 150 mA cm^?2 and a Tafel slope of 23.3 mV dec^?1 in 1.0 M KOH solution. Electron transfer from NiFe-LDH to NiMoP at the nanointerface reduces the energy barrier of the catalytic process, thus improving the OER activity performance. Thus, high-efficiency electrocatalysts can be utilised by constructing heterojunctions to regulate the electronic structure at the interface of the electrocatalysts.     

Controlled galvanic decoration boosting catalysis: Enhanced glycerol electro-oxidation at Cu/Ni modified macroporous films

We report on glycerol electro-oxidation in alkaline medium at macroporous Ni electrodes decorated with Cu particles. Macroporous Ni film is electrodeposited, using hydrogen bubbles as dynamic templates, atop of a Cu substrate. This film shows good electrocatalytic activity towards glycerol oxidation reaction (GOR). The Ni film is further decorated with Cu via spontaneous deposition from CuSO₄ solution. This is done to enhance the catalytic activity of the film towards GOR. The morphology of the Cu-decorated Ni film is controlled using various additives such as KCl and (NH₄)₂SO₄ which are added to the Cu deposition bath. The as-prepared Cu-decorated Ni films are characterized by electrochemical measurements, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). It is found that these additives have tremendous effects on the morphology and the electrocatalytic activity of the decorating Cu particles.The decorated Ni foam showed superior electrocatalytic activity towards the GOR, as confirmed by the negative shift in the onset oxidation potential (ca. 100 mV) together with an increase in oxidation current that is up to 1.5-fold during the cyclic voltammetry (CV) measurements, compared to the undecorated Ni foam.     

Hierarchical NiMo alloy microtubes on nickel foam as an efficient electrocatalyst for hydrogen evolution reaction

Developing efficient, non-noble electrocatalysts for hydrogen evolution reaction (HER) is of high significance for future energy supplement, but challenging. NiMo alloy is a non-noble-metal-based efficient catalyst for HER due to its appropriate hydrogen binding energy and excellent alkali corrosion resistance. Herein, for the first time, we report the preparation of radially aligned NiMo alloy microtubes on Ni foam (NiMo MT/NF). The synthesized NiMo alloy catalyst was composed of the Ni₁₀Mo phase; notably, this hierarchically structured material possessed abundant active sites and a high surface area, and exhibited efficient electronic transport properties. The NiMo MT/NF electrode exhibited a low overpotential of 119 mV at 10 mA/cm² in a base solution, which was 50 mV less than that of NiMo alloy nanoparticles on NF (169 mV).     

Well-dispersed Pt nanodots interfaced with Ni(OH)2 on anodized nickel foam for efficient hydrogen evolution reaction

Hindered by price and scarcity, the exploitation of supported Pt-based electrocatalysts with Pt single atoms or Pt nanoclusters is an alternative way to decrease the dosage of Pt and improve the electrocatalytic performance for hydrogen evolution reaction (HER) of water splitting. The anodization technology is used to modify the surface of nickel foam (NF) to form the porous NiF₂ network structure. Then Pt nanodots interfaced with Ni(OH)₂ (Pt/Ni(OH)₂) hybrid on the anodized NF has been in-situ synthesized by a simple hydrothermal decomposition method. Results show that Pt nanodots on the substrate have good dispersion with the average size of 3 nm, and the Pt loading is only 0.229 mg cm⁻². The prepared electrode exhibits the low overpotentials of 25.9 mV and 211 mV at the current densities of 10 and 100 mA cm⁻², respectively, a small Tafel slope of 37.6 mV dec⁻¹, and the excellent durability for HER. The porous network nanostructure of Pt/Ni(OH)₂ hybrid, the large electrochemical surface area, the fast facilitated electron transport capability, and the firm adhesion of Pt nanodots with the anodized NF substrate contribute to the remarkable performance towards HER.     

Preparation of Ni–P–La alloy as a novel electrocatalysts for hydrogen evolution reaction

Ternary Ni–P–La alloy was synthesized by the co-electrodeposition method on the copper substrate. The energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), and X-ray diffraction (XRD) were used for characterization of the synthesized alloy. The electrochemical performance of the novel alloy was investigated based on electrochemical data obtained from steady-state polarization, Tafel curves, linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline solution and at ambient temperature. The results showed that the microstructural properties play a vital purpose in determining the electrocatalytic activity of the novel alloys. Also, the HER on investigated alloys was performed via the Volmer-Heyrovsky mechanism and Volmer step as RDS in this work. Ni–P–La catalyst was specified by ƞ₂₅₀ = −139.0 mV, b = −93.0 mV dec⁻¹, and j_o = −181.0 μA cm⁻². The results revealed that the Ni–P–La catalysts have a high potential for HER electrocatalysts in 1M NaOH solution.     

Gold nanoparticle-coated Ni/Al layered double hydroxides on glassy carbon electrode for enhanced methanol electro-oxidation

We report a facile electrochemical strategy for the synthesis of Ni/Al layered double hydroxides (LDHs) and gold nanoparticle (AuNPs)-coated glassy carbon electrode (GCE). The new electrode is named LDH/AuNPs/GCE. The new electrode is named LDH/AuNPs/GCE. The electrocatalytic activity of LDH/AuNPs toward methanol electro-oxidation was studied by cyclic voltammetry and chronoamperometry. Compared to the Ni/Al-LDH modified GCE without AuNPs film (LDH/GCE), the LDH/AuNPs/GCE exhibits remarkably higher catalytic activity for methanol electro-oxidation, e.g. the lower oxidation potential (0.57 V vs. SCE) and the higher current density (6-fold). The enhancement may be attributed to the higher electrocatalytic activity of Ni/Al-LDHs in the presence of AuNPs, the synergy effect between them, or both. The results presented here may be of broad interest not only for developing fuel cells but also for understanding of OH⁻ electro-generated on noble metal surfaces.     

Effect of pore orientation on the catalytic performance of porous NiMo electrode for hydrogen evolution in alkaline solutions

Porous NiMo alloys with Mo content of 5 at.% were fabricated by freezing casting method. The pores are elongated, and the media pore size is 8.1 μm. The electrocatalytic activity of the synthesized NiMo alloy foam as cathodes for hydrogen evolution reaction (HER) in 6.0 M potassium hydroxide solution was investigated. Results show that the electrodes which pore orientation is parallel to the hydrogen overflow direction present higher electrocatalytic activity than the electrodes with pore orientation perpendicular to the hydrogen overflow direction. The Tafel slope is 94 and 117 mV dec⁻¹, respectively at a current density of 10 mA/cm² at room temperature.     

A non-noble,low cost,multicomponent electrocatalyst based on nickel oxide decorated AC nanosheets and PPy nanowires for the direct methanol oxidation reaction

The multicomponent electrocatalyst is a low-cost composite material exhibiting excellent catalytic activity suitable for methanol oxidation reactions (MOR). In this work, we report a glassy carbon electrode modified nickel oxide nanospheres (NiO) decorated biomass-derived activated carbon (AC) nanosheets and polypyrrole (PPy) nanowire, electrocatalyst (NiO_AC@PPy/GCE) for direct methanol oxidation fuel cell (DMFC) application. The SEM micrographs reveal the nanosheets and nanowire-like morphology of AC and PPy decorated with NiO nanospheres which provide a high surface area with electrocatalytic activity, and stability for MOR. The NiO_AC@PPy/GCE exhibits a high current density of 551 mA/mg at a low onset potential of 0.5 V (vs Ag|AgCl) towards electro-oxidation of 0.5 M methanol (MeOH) in an alkaline medium. This superior performance of the NiO_AC@PPy/GCE over other reported metal-oxides based electrocatalysts is attributed to the synergistic effect of the NiO_AC@PPy electrocatalyst, wherein NiO provides electrocatalytic active sites for MOR via Ni²⁺/Ni³⁺ redox couple while the PPy and AC contribute towards the chemical stability and electrical conductivity of the electrode, respectively. The electrode shows 79% of capacity retention after 10,000 s of chronoamperometry displaying excellent chemical stability with reduced effect of CO intermediate poisoning at the electrode surface. This excellent stability and overall performance of the NiO_AC@PPy proves it as an ideal, low-cost non-noble electrocatalyst for DMFCs.     

Hydrogen evolution assisted electrodeposition of bimetallic 3D nano/micro-porous PtPd films and their electrocatalytic performance

Self-supporting PtPd bimetallic catalysts with three-dimensional (3D) porous structures and a greatly enhanced surface area are firstly fabricated at a glassy carbon electrode (GCE) by a one-step strategy of potentiostatic co-electrodeposition utilizing hydrogen bubble dynamic templates. The atomic ratio of Pt/Pd in the bimetallic catalysts is varied by changing the composition of the electrodeposition solution. The 3D porous PtPd films are characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) and examined as electrocatalysts for the electro-oxidation of methanol using cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). Experimental results demonstrate that a small amount of Pd plays the predominant role in the formation of 3D porous structure for PtPd bimetallic catalysts and is an excellent catalytically enhancing agent for the Pt catalyst towards methanol electro-oxidation. The study on electrocatalytic performance of mono and bimetallic catalysts towards formic acid electro-oxidation also reveals the better activity of 3D porous Pd film for this reaction.     

Designing of noble metal free high performance mesoporous electrocatalysts for water splitting

The work undertaken involved the synthesis of mesoporous M-ferrites (M = Co, Ni) by facile PEG-assisted microemulsion method and exploration of their electrocatalytic potential for water splitting. The onset potential for oxygen evolution befalls at nearly 1.53 V_RHE (η = 300 mV), which is 400–450 mV lesser than those reported for simple ferrites and iron oxides thin-film as electrocatalysts. These electrocatalysts exhibit the good electroactive zone having the lowest Tafel slope value, 68 mVdec⁻¹, as compared to that reported for nickel and cobalt based materials. High TOF value is attributed to the superior catalytic activity of the catalysts. NiFe₂O₄ exhibits the turn over frequency (TOF) of 2.4 s⁻¹ just at overpotential value of 0.42 V_RHE with 1.2 μmol of the prepared sample used in electrochemical analysis. The long-term catalytic stability of Ni and Co-Ferrites spectacle a remarkable and stable current density of >15 mAcm⁻² for oxygen evolution and maintained for several hours.     

Electrochemical construction of Cu@NF frameworks and synthesis of self-supported microflower Cu2S@NF as bifunctional catalysts for overall water splitting

A two-step electrochemical method is proposed for the in-situ deposition of copper and synthesis of copper(Ⅰ) sulfide (Cu₂S) with controllable morphology on nickel foam (NF), and the thus-prepared self-supported Cu₂S@NF electrodes exhibit excellent performance as bifunctional electrocatalysts. Characterizations with scanning electron microscopy show rock-shape of the deposited copper through potentiostatic method, which can be further sulfurized to microflower morphology by a unique underpotential electrochemical method. The size and amount of the deposits can be adjusted by controlling applied potentials, leading to the optimization of electrocatalytic activity. The Cu₂S@NF exhibits superior electrocatalytic performance towards HER and OER in 1 M KOH with the low overpotentials of 105 mV and 194 mV at 10 mA/cm², as well as small Tafel slopes of 92.89 mV/dec and 72.81 mV/dec, respectively. This work provides a simple method for the synthesis of efficient catalysts, which can be extended to the fabrication of other transition metal-based electrocatalysts.     

Phosphatized pseudo-core-shell Ni@Pt/C electrocatalysts for efficient hydrazine oxidation reaction

In this study, a series of phosphatized pseudo-core-shell Ni@Pt/C electrocatalysts has been obtained for efficient hydrazine oxidation reaction (HzOR). These (Ni@Pt–P/C) electrocatalysts were prepared by a primary replacement method followed by subsequent phosphating process. Among all Ni@Pt–P/C electrocatalysts, as-prepared Ni@Pt–P/C-400 electrocatalyst shows the highest HzOR performance (515 mA mg⁻¹_Pt), best stability, durability and lowest activation energy (12.60 kJ mol⁻¹). The satisfactory HzOR performance is mainly resulted from the unique design of phosphating effect on core-shell structure which producing good synergistic effect between Ni, P and Pt. This work would pave a way for developing other low-Pt catalysts in the future.