One-step gas phase sulfided NiFe coating as self-supporting electrode for high efficiency oxygen evolution reaction

The development of cost-effective oxygen evolution reaction (OER) electrocatalytic electrodes is one of the essential means of applying green hydrogen energy. Due to the complex steps in the anodic OER, the high overpotential hinders the kinetics of water splitting. In this paper, the sulfided NiFe coating was innovatively designed as a self-supporting OER electrode by high-velocity oxygen fuel (HVOF) spraying coupled with one-step gas phase sulfuration. The thickness of the NiFe coating is approximately 20 μm. After the sulfuration treatment, the surface of the NiFe coating is remolded into a uniform rock sugar-like structure, and simultaneously forms new NiS and Ni₃S₄ phases. The sulfided NiFe coating electrode shows relatively low overpotentials of 220 mV and 253 mV at the current density of 10 mA cm⁻² and 100 mA cm⁻², respectively, and the Tafel slope is as low as 28.6 mV dec⁻¹. The excellent electrocatalytic activity is mainly attributed to the synergistic effect of sulfides, the adsorption of OH⁻ by the Ni³⁺ in alkaline electrolyte, and the acceleration of O₂ separation by the S²⁻ through promoting the cleavage of O–O bonds. In addition, the sulfided NiFe coating electrode also has a small charge transfer resistance, and the potential stability is as high as 98.1% in the 70 h stability test. Therefore, the development of sulfided transition metal coating electrodes can provide a new idea for the large-scale industrialization of water splitting.     

Ni3S2-MoSx nanorods grown on Ni foam as high-efficient electrocatalysts for overall water splitting

In order to solve the problem of large overpotential in water electrolysis for hydrogen production, transition metal sulfides are promising bifunctional electrocatalysts for hydrogen evolution reaction/oxygen evolution reaction that can significantly reduce overpotential. In this work, Ni₃S₂ and amorphous MoS_x nanorods directly grown on Ni foam (Ni₃S₂-MoS_x/NF) were prepared via one-step solvothermal process, which were used as a high-efficient electrocatalyst for overall water splitting. The Ni₃S₂-MoS_x/NF composite exhibits very low overpotentials of 65 and 312 mV to reach 10 mA cm⁻² and 50 mA cm⁻² in 1.0 M KOH for HER and OER, respectively. Besides, it exhibits a low Tafel slope (81 mV dec⁻¹ for HER, 103 mV dec⁻¹ for OER), high exchange current density (1.51 mA cm⁻² for HER, 0.26 mA cm⁻² for OER), and remarkable long-term cycle stability. This work provides new perspective for further the development of highly effective non-noble-metal materials in the energy field.     

Novel 13X Zeolite/PANI electrocatalyst for hydrogen and oxygen evolution reaction

In this work, first 13X zeolite was prepared by the hydrothermal method. Then, the composite electrode was fabricated by using 13X zeolite and aniline monomer in nickel foam by electropolymerization technique in an acidic medium (13X/PANI). The synthesized 13X zeolite was characterized by physicochemical characterization techniques such as Fourier transform infra-red (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) pattern and nitrogen sorption isotherm. 13X/PANI composite was further analyzed by XRD, XPS and FE-SEM techniques. Furthermore, the catalyst activity of the synthesized 13X, PANI and 13X/PANI composite electrodes was evaluated in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by using linear square voltammetry (LSV) and Tafel slope method. The Tafel slopes of HER were found to be 203 mV dec⁻¹, 440 mV dec⁻¹ and 282 mV dec⁻¹ for 13X, PANI and 13X/PANI-15 electrodes respectively. While the OER Tafel slopes were found to be 423 mV dec⁻¹, 310 mV dec⁻¹ and 168 mV dec⁻¹ for 13X, PANI and 13X/PANI-15, respectively. 13X/PANI-15 electrodes show excellent catalytic performance about the overpotential at 10 mA cm⁻² for HER and the overpotential at 20 mA cm⁻² for OER. The obtained results suggest fabricated novel electrodes are a potential candidate for HER and OER reaction and can be open new avenue for other electrochemical reactions.     

Hydrothermally/electrochemically decorated FeSe on Ni-foam electrode: An efficient bifunctional electrocatalysts for overall water splitting in an alkaline medium

A new hybrid catalyst based on Ni foam (NF) and FeSe was prepared by a facial hydrothermal method, in which Se-decorated NF was subsequently electrochemically doped by Fe. Binder-free catalyst containing electrodes were directly tested for the hydrogen and oxygen evolution reaction (HER/OER). The FeSe/NF electrode displayed an OER current density of 100 mA cm⁻² at potential of 1.42 V, and a relatively small Tafel slope of 109 mV dec⁻¹ in a 1 M KOH solution. Also, FeSe/NF electrode exhibited reasonable HER overpotential of 200 mV at 10 mAcm⁻² current density with Tafel slope of 145 mV dec⁻¹. The XRD and TEM studies revealed that the formation of heterogeneous interfaces of NiSe₂ and FeSe₂,generated more active sites that can promote better ions and electron transport in the electrode/electrolyte interfaces. Furthermore, HRTEM analysis indicates that FeSe₂ rich in Se vacancy defects can be created with suitable M − O and M − H bond for better OER and HER performance, respectively. In a-two electrode alkaline water electrolyzer, current densities of 10 mA cm⁻² and 50 mA cm⁻² were obtained at cell voltages of 1.52 V and 1.85 V, respectively, using pure FeSe–NF as both the cathode and anode.     

The 3D ultra-thin Cu1-xNixS/NF nanosheet as a highly efficient and stable electrocatalyst for overall water splitting

In recent years, the exploration of efficient and stable noble-metal-free electrocatalysts is becoming increasingly important, used mainly for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In this work, a new ultrathin porous Cu_1-xNi_xS/NF nanosheets array was constructed on the 3D nickel skeleton by two-step method: hydrothermal method and vulcanization method. Through these two processes, Cu_1-xNi_xS/NF has a larger specific surface area than that of foamed nickel (NF) and Cu_1-xNi_xO/NF. The Cu_1-xNi_xS/NF materials show excellent catalytic activity by accelerating the electron transfer rate and increase the amount of H₂ and O₂ produced. The lower overpotential was obtained only 350 mV at 20 mA cm⁻² for OER, not only that, but also the same phenomenon is pointed out in HER, optimal Cu_1-xNi_xS/NF presents low overpotentials of 189 mV to reach a current density of 10 mA cm⁻² in 1.0 M KOH for HER. Both OER and HER shows a lower Tafel slope: 51.2 mV dec⁻¹ and 127.2 mV dec⁻¹, subsequently, the overall water splitting activity of Cu_1-xNi_xS/NF was investigated, and the low cell voltage was 1.64 V (current density 10 mA cm⁻²). It can be stable for 14 h during the overall water splitting reaction. These results fully demonstrate that Cu_1-xNi_xS/NF non-precious metal materials can be invoked become one of the effective catalysts for overall water splitting, providing a richer resource for energy storage.     

Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis

The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm⁻² and a low Tafel slope of 45 mV dec⁻¹. In OER, the optimized sample performs better than a state-of-the-art RuO₂ catalyst and produces an overpotential of 337 mV at 10 mA cm⁻², lower than that of RuO₂. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in overall water splitting.     

Ni/NiO@rGO as an efficient bifunctional electrocatalyst for enhanced overall water splitting reactions

Herein, we fabricated bifunctional, noble metal-free, highly efficient nickel/nickel oxide on reduced graphene oxide (Ni/NiO@rGO) by chemical synthesis approach for electrochemical water splitting reaction. Its structural and morphological characterization using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), energy dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD) represents, Ni/NiO@rGO is having Ni/NiO NPs ∼10 nm (±2 nm) on graphene oxide with face-centered cubic (FCC) crystal structure. Moreover, the presence of Ni/NiO (2.26%), O (6.56%), N (0.74%) and C (90.44%) from EDAX analysis further confirms the formation of Ni/NiO@rGO and it also supported by FTIR studies. This nanocatalyst is examined further for electrocatalytic water splitting reactions (HER and OER). It demonstrated low overpotential 582 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 63 mV dec⁻¹ obtained in 0.5 M H₂SO₄ towards HER. Also, at the other end at onset potential of 1.6 V vs. RHE towards OER. It demonstrated low overpotential 480 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 41 mV dec⁻¹ in 0.5 M KOH towards OER observed. Hydrogen fuel is eco-friendly to the environment and noteworthy performance of earth-saving reactions.     

Tailoring Cr doped NiFeP nanoparticles embedded in 3D cellulose nanofibrils carbon architecture for efficient oxygen evolution reaction

Oxygen evolution reaction (OER) is considered the bottleneck that restricting the pace of electrocatalytic hydrogen production. Modulating structure and heterogeneous doping are essential approaches to effectively promote the electrocatalytic efficiency and stability. Herein, three-dimensional (3D) porous Cr doped NiFeP nanoparticles encapsulated in cellulose nanofibrils (CNF) carbon architecture (Cr–NiFeP/NC) with high-efficiency and durable OER performance was constructed. CNF played crucial role on the construction of 3D porous framework and promoting the OER performance significantly. Benefiting from the 3D porous structure, high specific surface area and exposed abundant active sites, the Cr–NiFeP/NC electrocatalyst displayed excellent OER performance, which the overpotential to deliver the current density of 10 mA cm⁻² was only 249 mV with a Tafel slope of 51.2 mV dec⁻¹ in 1.0 M KOH, outperforming the RuO₂ and other reported electrocatalysts remarkably. In addition, the Cr–NiFeP/NC electrocatalyst exhibited outstanding stability, which the overpotential was only increased by 2.5% after 48 h chronopotential measurement to deliver a current density of 10 mA cm⁻² with stable morphology and structure. This work demonstrated an integrated strategy of Cr doping and 3D porous structure modulating employed CNF as skeleton for the efficient and durable OER performance, providing a spark for hydrogen production by water splitting.     

In situ surface dealumination of intermetallic NiFe aluminides electrocatalysts for enhancing the oxygen evolution

Herein, based on the mechanical alloying (MA) and in situ electrochemical etching methods, a series of porous Ni–Fe electrocatalysts with different Ni/Fe atomic ratios derived from intermetallic NiFe aluminides have been designed and applied to OER (oxygen evolution reaction) in alkaline solution. As comparing with bulk NiFe aluminides electrocatalyst, the porous electrocatalyst presents higher activity via the etching method. In addition, among all porous samples with different metal stoichiometric ratios, Ni_2/3Fe_1/3Al shows the highest OER activity with an overpotential of 299 mV at 10 mA cm^?2 and a Tafel slope of 58.9 mV dec^?1, which can be attributed to the high intrinsic activity and large electrochemical surface area from the leaching of Al. This work provides a promising route to in situ synthesize highly efficient electrocatalysts for water splitting.     

A novel efficient dual-functional electrocatalyst for overall water splitting based on Ni0.85Se/RGO/CNTs nanocomposite synthesized via different nickel precursors

Synthesizing efficient and affordable electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a crucial problem on the way to practical applications for producing clean H₂ fuel. Herein, high-efficiency and stable transition metal based electrocatalysts Ni_0.85Se-1, Ni_0.85Se-2 and Ni_0.85Se-3 materials with different morphological characteristics were derived via a one-step hydrothermal route using the Ni(OH)₂ and metal-organic framework (Ni-BDC and Ni-BTC) as precursors, respectively. The results showed that Ni_0.85Se-2 exhibited excellent electrocatalytic activity. Subsequently, introducing carbon nanomaterials (RGO and CNTs) to form Ni_0.85Se/RGO/CNTs nanocomposite material further improves the catalytic activity owing to high conductivity. The resulting Ni_0.85Se/RGO/CNTs nanocomposites electrocatalyst showed a low overpotential of 232 mV and 165 mV and a low Tafel slope of 64 mV dec^?1 and 98 mV dec^?1 when the current density was 10 mA cm^?2 for OER and HER, respectively. In addition, the Ni_0.85Se/RGO/CNTs nanocomposites were used as an anode and cathode of the water electrolysis device and the overall water splitting performance was investigated. The results show just a voltage of 1.59 V was required when the current density was 10 mA cm^?2 and good overall water splitting stability for 20 h. The outstanding electrocatalytic performance of Ni_0.85Se/RGO/CNTs is mostly due to its noticeable porous structure, the high conductivity and the large surface area that came from RGO and CNTs.     

Defect-induced FexNi1-xSe2 nanoparticles based electrocatalysts towards enhanced hydrogen and oxygen evolution reactions

Transition metal selenides are regarded as promising materials for the production of clean energy through electrocatalytic water splitting. Creation of defects in these metal selenides is one of the prudent strategies to enrich the active sites which in turn enhances the electrocatalytic activity of these materials and makes them viable for broader applications. Herein, defect-induced, iron-doped nickel selenide nanoparticles were prepared for the first time and their electrocatalytic efficacy towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been demonstrated. Fe_xNi_1-xSe₂ nanoparticles (x = 0.25, 0.50, 0.75) were prepared using a facile hydrothermal method, in which defects were induced by annealing at 300 °C to obtain DI-Fe_xNi_1-xSe₂. The structural and morphological investigations confirmed the size reduction and creation of defects after annealing, without any significant change in the crystal structure, which in turn is expected to promote the electrocatalytic activity. Accordingly, among all the materials investigated, DI-Fe_0.25Ni_0.75Se₂ has shown the highest HER activity in 0.5 M H₂SO₄ at a lesser overpotential of 128 mV at 10 mA cm^?2 and the Tafel slope was calculated to be 37.9 mV dec^?1. Interestingly, the same material has displayed high performance towards OER in 1 M KOH with a lesser overpotential at 205 mV and a Tafel slope of 55.5 mV dec^?1. Thus obtained electrocatalytic activity was much better than the reported nickel selenide based electrocatalysts. Further, the DI-Fe_0.25Ni_0.75Se₂ electrocatalyst has demonstrated impressive stability in the acidic and alkaline medium during continuous electrolysis even up to 12 h.     

Phase pure synthesis of iron-nickel nitride nanoparticles: A low cost electrocatalyst for oxygen evolution reaction

Synthesis of mixed transition metal nitrides often leads to the formation of more than one phases in the final product. A control over molar ratio of metals (Fe:Ni) along with synthetic strategy is used to form phase pure product (Fe₃Ni₇N@C). The synthesized material is used as an efficient and cost-effective electrocatalyst for oxygen evolution reaction (OER). Fe₃Ni₇N@C requires a low overpotential of 290 mV to achieve a catalytic current density of 10 mA cm⁻² which holds Tafel slope of 40 mV dec⁻¹ superior to the noble metal benchmark catalysts. The physicochemical integrity of Fe₃Ni₇N@C is maintained up to 12 h activity as evident from post catalytic characterization.     

Cobalt phosphide nanoparticles embedded in 3D N-doped porous carbon for efficient hydrogen and oxygen evolution reactions

An electrocatalyst based on a unique three-dimensional (3D) N-doped porous carbon sheet networks embedded with CoP₂ nanoparticles (CoP₂@3D-NPC) was synthesized by a facile pyrolysis process as well as an in-situ phosphatization method. The improved CoP₂@3D-NPC hybrid materials show excellent electrocatalytic activity toward HER and OER. This material provides a low overpotential of 126 mV at 10 mA cm⁻² in 0.5 M H₂SO₄ and 167 mV at 20 mA cm⁻² in 1.0 M KOH for HER with a small Tafel slope value of 59 mV dec⁻¹, respectively. Besides, it is also active for the OER under alkaline conditions. Such a prominent property of the CoP₂@3D-NPC electrocatalyst could be attributed to its excellent electrical conductivity of 3D carbon substrate, strong synergistic effect between CoP₂ nanoparticles and carbon nanosheet as well as extra active sites created by the N-doped structure.     

One-pot preparation of Ni3S2@3-D graphene free-standing electrode by simple Q-CVD method for efficient oxygen evolution reaction

Efficient non-noble metal catalysts for the oxygen evolution reaction (OER) are particularly important in the practical applications of electrocatalytic water splitting (ECWS). Herein, based on a simple quasi chemical vapor deposition (Q-CVD) method, we fabricate a newly Ni₃S₂@3-D graphene free-standing electrode for efficient OER applications. The Ni₃S₂@3-D graphene integrates the advantageous features of 3-D graphene and Ni₃S₂ towards OER, such as more interfacial catalytic sites, pore-rich structure, N-doped structure and good electrical conductivity. Benefiting from the favorable features, the Ni₃S₂@3-D graphene (especially 900 °C sample) exhibits excellent OER performances in alkaline medium, which includes a low on-set potential (1.53 V), low overpotential of 305 mV at a current density of 10 mA cm⁻², and a smaller Tafel slope (50 mV dec⁻¹). This catalyst also shows ultrahigh stability after chronoamperometry response at 10 mA cm⁻² for 48 h with 30% increase in the current density. The present work opens a new approach for the one-pot construction of hybrid materials between metal sulfide and graphene to increase the electrocatalytic activity of non-noble metal OER catalysts.     

Rapid synthesis of porous Ni/Co/Fe-LDHs nanosheets for effective electrochemical oxygen evolution reaction and zinc-air batteries

Transition metal compounds, especially layered double hydroxide materials (LDHs), show excellent catalytic activity in oxygen evolution reaction (OER). The ethanol oxidation reaction (EOR) is an innovative alternative anodic reaction to OER for improving the efficiency of water splitting to produce hydrogen. In order to improve the reactivity and explore the similarities and differences of active sites in the two reactions, three kinds of porous LDHs (NiFe, NiCo, CoFe LDHs) were synthesized and a series of tests were carried out. Among them, the best performing OER catalyst is NiFe-LDHs with a low overpotential of 1.44 V vs. RHE at 10 mA cm^?2 and a Tafel slope of 23.85 mV dec^?1. As for the EOR reaction, NiCo-LDHs is the best, with an overpotential of only 1.38 V vs. RHE at 10 mA cm^?2 and a Tafel slope of 71.58 mV dec-1. In addition, compared with OER, the LHDs material exhibited better stability in the EOR. This work provides a new direction for studying the electrocatalytic activity of LDHs materials in OER and EOR.     

Accelerated oxygen evolution kinetics on NiFeAl-layered double hydroxide electrocatalysts with defect sites prepared by electrodeposition

NiFe layered double hydroxides (LDHs) is considered to be one of the LDHs electrocatalyst materials with the best electrocatalytic oxygen evolution properties. However, its poor conductivity and inherently poor electrocatalytic activity are considered to be the limiting factors inhibiting the electrocatalytic properties for oxygen evolution reaction (OER). The amorphous NiFeAl-LDHs electrocatalysts were prepared by electrodeposition with nickel foam as the support, and the D-NiFeAl-LDHs electrocatalyst with defect sites was then obtained by alkali etching. The mechanism of catalysts with defect sites in OER was analyzed. The ingenious defects can selectively accelerate the adsorption of OH⁻, thus enhancing the electrochemical activity. The D-NiFeAl-LDHs electrocatalyst had higher OER electrocatalytic activity than NiFe-LDHs electrocatalyst: its accelerated OER kinetics were mainly due to the introduction of iron and nickel defects in NiFeAl-LDHs nanosheets, which effectively adjusted the surface electronic structure and improved OER electrocatalytic performance. There was only a low overpotential of 262 mV with the current density of 10 mA cm⁻², and the Tafel slope was as low as 41.67 mV dec⁻¹. The OER electrocatalytic performance of D-NiFeAl-LDHs was even better than those of most of the reported NiFe-LDHs electrocatalysts.     

Mesoporous spinel NiFe oxide cubes as advanced electrocatalysts for oxygen evolution

Oxygen evolution reaction (OER) is the rate-controlling step of the electrochemical water splitting. The slow kinetics hinders large-scale H₂ production. Herein, the spinel NiFe oxides were prepared by directly pyrolyzing nickel hexacynoferrate precursors in air. The NiFe oxides were presented as mesoporous nanocubes with a specific surface area of 125 m² g⁻¹. The mesoporous spinel NiFe oxide nanocubes can afford a geometric current of 10 mA cm⁻² at a low overpotential of a 0.24 V and a small Tafel slope of 41 mV dec⁻¹ in alkaline solution. The specific activity can reach up to 0.37 mA cm⁻² with a turnover frequency of 0.93 s⁻¹. The superior OER activity of the NiFe oxide nanocubes (NiFeO NCs) can outperform those of the state-of-the-art IrO₂ catalysts, and compare favorably with other spinel transition metal oxides reported recently under identical condition. NiFeO NCs also show a long-term durability without significant loss of the OER activity. Our works provide a new strategy to develop efficient, robust and earth-abundant spinel NiFe oxides as advanced OER electrocatalysts to replace the expensive commercial IrO₂ catalysts for water splitting in the industrial scale.     

Interface regulation of Pt quantum dots doped nickel phosphide and cobalt hydroxide to promote electrocatalytic overall water splitting

The transition metal phosphates are earth-abundant minerals that have been shown to perform well in electrocatalytic water splitting, whereas these catalysts still tend to have excessively high overpotentials and slow kinetics in HER and OER processes. In the present work, hybrid catalysts consisting of Pt quantum dots doped NiP (NiP-Pt) nano-embroidery spheres and Co(OH)₂ nanosheets were successfully prepared by two-step electrodeposition method. The excellent catalytic performance of the catalyst relies principally on the synergistic interaction between NiP and Pt quantum dots. Additionally, the NiP-Pt exhibits strong electronic interactions at the interface with Co(OH)₂. Consequently, the catalyst has a strong catalytic performance in terms of HER and OER catalytic performance. In terms of HER, an overpotential of only 40 mV is required when the current density reaches 10 mA cm^?2, corresponding to a Tafel slope of 49.85 mV·dec^?1. At the same time, the catalyst also performs well at OER, with a current density of 10 mA cm^?2 at an overpotential of 186 mV and a Tafel slope of 53.049 mV·dec^?1 much less than most electrocatalysts. This study involving electrodeposition and doping of quantum dots provides a new idea for the efficient synthesis of fundamental HER and OER bifunctional catalysts.     

Co0.85Se on three-dimensional hierarchical porous graphene-like carbon for highly effective oxygen evolution reaction

Designing an efficient, cheap and abundant catalyst for oxygen evolution reaction (OER) is crucial for the development of sustainable energy sources. A novel catalyst which could be a promising candidate for such electrocatalysts is described. Co_0.85Se supported on three-dimensional hierarchical porous graphene-like carbon (HPG) exhibits outstanding catalytic performances for OER in alkaline medium. It is found that the onset overpotential is 311 mV on the Co_0.85Se/HPG electrode, which is more 28 and 41 mV negative than that on the Co/HPG and Co₃O₄/HPG electrodes. What's more, the value of Tafel slope is 61.7 mV dec⁻¹ and the overpotential at the current density of 10 mA cm⁻² is 385 mV on this electrode. The Co_0.85Se/HPG of this work is an appealing electrocatalyst for OER in basic electrolyte.     

Carbon nanorod supported metal alloy nanocubes using polydopamine as location reagent for water splitting

Transition metal catalysts were supposed to be the most likely substitute for commercial noble metal catalysts, and the development of highly active and long-term catalyst for water splitting are the future trend. Herein, Ni rectangular nitrogen doped carbon nanorods@Fe–Co nanocubes (Ni-CNRs@Fe–Co cubes) were fabricated via a facile template-free method. This simple strategy not only realizes the structure tailoring, but also achieves high-quality nitrogen-doping. Specifically, nickel dimethylglyoxime [Ni(dmg)₂] with rectangular rodlike structure was firstly synthesized by solution method, then metal-organic frameworks Fe–Co nanocube with different contents were loaded on rectangular carbon nanorods with polydopamine as the locating and the connecting agent, and finally Ni-CNRs@xFe-Co cubes were obtained by a one-step calcination. A series of electrochemical tests were researched on materials with different metal contents in the 1 M KOH solution. The Ni-CNRs@Fe–Co cubes show excellent electrocatalytic activity in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). For HER and OER, the Tafel slopes were 83.3 mV dec⁻¹ and 71 mV dec⁻¹, the onset potential were −167 mV and 1.62 V, and reached the current densities of 10 mA cm⁻², the overpotential just needed 196 mV and 433 mV, respectively. This novel synthetic strategy will provide a template-free way for cheap electrocatalysts of non-precious metal for OER and HER.