Ideal Electrocatalysts Research Articles

Conductive Metal-Organic Frameworks with Extra Metallic Sites as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

The 2D conductive metal–organic frameworks (MOFs) are expected to be an ideal electrocatalyst due to their high utilization of metal atoms. Exploring a new conjugated ligand with extra active metallic center can further boost the structural advantages of conductive MOFs. In this work, hexaiminohexaazatrinaphthalene (HAHATN) is employed as a conjugated ligand to construct bimetallic sited conductive MOFs (M23(M13∙HAHATN)2) with an extra M–N2 moiety. Density functional theory (DFT) calculations demonstrate that the 2D conjugated framework renders M23(M13∙HAHATN)2 a high electric conductivity with narrow bandgap (0.19 eV) for electron transfer and a favorable in‐plane porous structure (2.7 nm) for mass transfer. Moreover, the metal atom at the extra M–N2 moiety has a higher unsaturation degree than that at M–N4 linkage, resulting in a stronger ability to donate electrons for enhancing electroactivity. These characteristics endow the new conductive MOFs with an enhanced electroactivity for hydrogen evolution reaction (HER) electrocatalysis. Among the series of M23(M13∙HAHATN)2 MOF, Ni3(Ni3∙HAHATN)2 nanosheets with the optimal structure exhibit a small overpotential of 115 mV at 10 mA cm−2, low Tafel slope of (45.6 mV dec−1), and promising electrocatalytic stability for HER. This work provides an effective strategy for designing conductive MOFs with a favorable structure for electrocatalysis.

Challenge of advanced low temperature fuel cells based on high degree of freedom of group 4 and 5 metal oxides

To obtain an ideal electrocatalysts for hydrogen fuel cells, we investigated group 4 and 5 oxide-based compounds because of their high degree of freedom. First-principles calculations revealed that oxide surfaces such as those of titanium oxide could break down the universal scaling to achieve the ideal state of the oxygen reduction reaction. We experimentally clarified that the active sites were oxygen vacancies for tantalum and zirconium oxides, in addition to doped foreign elements and crystalline structures for titanium oxide. We successfully demonstrated that precious metal-free and carbon-free oxide-based cathodes have high quality active sites and superior durability in 0.1 M sulfuric acid at 80°C. Our strategy was developed as follows: (1) Active sites are created on the oxide surface by modifying the crystalline structure and electronic states and (2) electrons participating in the oxygen reduction reaction are supplied by nanosized oxide particles and oxide films through the tunneling effect of electrons.

One-Step Synthesis of N, P-Codoped Carbon Nanosheets Encapsulated CoP Particles for Highly Efficient Oxygen Evolution Reaction.

Oxygen electrocatalysis, especially oxygen evolution reaction (OER), is a central process during the actual application of rechargeable metal-air battery. It is still challenging to develop ideal electrocatalysts to substitute the commercial noble metal-based materials. In this work, we have constructed a new material, CoP nanoparticles, which are encapsulated by a biomolecule-derived N, P-codoped carbon nanosheets via a simple and facile one-step strategy. The as-prepared material releases a high electrocatalytic activity and stability for OER, with an overpotential of 310 mV to achieve 10 mA/cm2 in 1 M KOH. Importantly, we found that the phosphoric acid can not only introduce phosphorus dopant into 2D N-doped carbon nanosheets and play a role of pore-forming agent, but also participate in the formation of active center (cobalt phosphide). Moreover, the coverage of N, P-doped carbon can prevent the CoP nanoparticles from corrosion under the harsh reaction medium to achieve high and stable activity. We believe that our strategy can offer a novel pathway to synthesize new transition metal-based catalysts for electrocatalysis or other heterogeneous catalysis.

Deep Phase Transition of MoS2 for Excellent Hydrogen Evolution Reaction by a Facile C-Doping Strategy.

Metallic 1T-phase MoS2 is considered to be the ideal electrocatalyst to carry out hydrogen evolution reaction (HER) because of favorable conductivity and sufficient active site compared with 2H-phase MoS2. Nevertheless, 1T-phase MoS2 is conventionally synthesized in a complicated process, with the production of an unstable product, which hinders their practical applications. Herein, we propose a facile approach through a carbon-doping-induced phase transition to obtain highly stable 1T-2H mixed MoS2 nanosheets. The phase transition process is characterized by Raman and X-ray photoelectron spectroscopy, as well as high-resolution transmission electron microscopy images and delivers a high phase purity of ∼60% for 1T-MoS2. According to density functional theory simulations and experimental results, C-doped 1T-2H mixed MoS2 has the advantages of abundant active sites, facilitated charge transfer rate, and high activity toward HER. The obtained C-doped MoS2 exhibits a superb HER electrocatalytic performance, with a current density of 10 mA cm-2 and the overpotential as low as 40 mV in 1 M KOH solution, and brilliant stability.

Adsorption and catalytic activation of N2 molecule on iron dimer supported by different two-dimensional carbon-based substrates: A computational study

Transition metal dimers could exhibit unique electronic properties and better catalytic performance than single metal atom, thus making them attractive to catalyze some chemical reactions, in which the substrate could have prominent influences on their catalytic activity. In this work, the substrate effects of several two-dimensional (2D) carbon-based nanosheets on the adsorption and activation of N2 molecule on their supporting iron dimer (Fe2) were investigated by performing density functional theory (DFT) calculations. Our results showed that the Fe2 cluster can be stably anchored at the defect sites of these 2D carbon-based nanomaterials, thus leading to the accumulation of more positive polarized charges on the supported Fe2 cluster to promote the adsorption and activation of N2 molecule. Interestingly, the g-C3N4 supported Fe2 cluster is predicted to have excellent catalytic activity for converting the activated N2 to ammonia due to the small limiting potential (−0.32 V). Therefore, by choosing a suitable substrate, the Fe2 cluster can be utilized as an ideal electrocatalyst to activate and catalyze the inert N2 molecule.

Modulation of Phosphorene for Optimal Hydrogen Evolution Reaction.

Economical and highly effective catalysts are crucial to the electrocatalytic hydrogen evolution reaction (HER), and few-layer black phosphorus (phosphorene) is a promising candidate because of the high carrier mobility, large specific surface area, and tunable physicochemical characteristics. However, the HER activity of phosphorene is limited by the weak hydrogen adsorption ability on the basal plane. In this work, optimal active sites are created to modulate the electronic structure of phosphorene to improve the HER activity and the effectiveness is investigated theoretically by density-functional theory calculation and verified experimentally. The edges and defects affect the electronic density of states, and a linear relationship between the HER activity and lowest unoccupied states (εLUS) is discovered. The medium εLUS value corresponds to the suitable hydrogen adsorption strength. Experiments are designed and performed to verify the prediction, and our results show that a smaller phosphorene moiety with more edges and defects exhibits better HER activity and surface doping with metal adatoms improves the catalytic performance. The results suggest that modified phosphorene has large potential in efficient HER and provides a convenient standard to explore ideal electrocatalysts.

High-performance corrosion-resistant fluorine-doped tin oxide as an alternative to carbon support in electrodes for PEM fuel cells

The advent of new technologies and growing demand for fuel cell innovation has led to the development of novel non-carbon material strategies with inherent electrical conductance and corrosion resistance. Problems are often observed with carbon-based support materials, due to their limited electrochemical stability. The emphasis is therefore on fabricating high-performance, stable non-carbon alternatives that exhibit advantageous electrochemical properties compared to conventional carbon black, and are thus regarded as ideal electrocatalyst support materials. In this work, we investigated the influence of dopants, and the morphology of conductive, porous doped tin-based oxides, on corrosion resistance and electrical conductivity for fuel cell electrode applications. Among the various doping elements, fluorine anion doping into tin oxide plays a key role in the formation of such structures as a complexing agent for improving electrical conductivity and suppressing electrochemical dissolution processes. When used in polymer electrolyte membrane fuel cells with platinum electrocatalyst loading, fluorine tin oxide nanotubes exhibit not only cell performance comparable to that of state-of-the-art commercial Pt/C, but also excellent cycling stability. The superior electrochemical performance and stability of this novel non-carbon support material is due to its unique features, i.e., excellent electrical conductivity, electrochemical corrosion resistance, and electronic and compressive strain effects due to strong metal-support interactions.

KOH-treated reduced graphene oxide: 100% selectivity for H2O2 electroproduction

H2O2 is an important chemical widely used in paper, textile, water treatment and other fields, while the current industrial anthraquinone pathway is not sustainable. Herein, a highly efficient electrocatalyst, reduced graphene oxide (rGO-KOH), applied for electrochemical H2O2 production was obtained by treating graphene oxide (GO) with KOH aqueous solution. Compared to KBH4-treated reduced graphene oxide (rGO-KBH4) made by KBH4 reduction method, rGO-KOH has more ether bonds (C–O–C) on the surface and a larger electrochemically active surface area. Benefiting from these advantages, rGO-KOH exhibits enhanced selectivity (∼100%) and mass activity for the oxygen reduction reaction through a two-electron pathway (ORR-2e) than rGO-KBH4. Meanwhile, rGO-KOH also shows the excellent durablity for (ORR-2e) in alkaline media. Thus, rGO-KOH may be an ideal electrocatalyst for H2O2 electroproduction.

Oxygen deficiency assisted synthesis of network-like tungsten carbide-carbon nanotubes composites for methanol oxidation

Abstract 3D network-like tungsten carbide-carbon nanotubes composites were in-situ synthesized by using W18O49 as the precursor. The sea urchin like W18O49 with abundant oxygen defects was designed and fabricated to act as not only the source of tungsten, but also the catalyst to initiate the growth of carbon nanotubes. Distinct from carbon nanotubes-supported tungsten carbide, the obtained tungsten carbide-carbon nanotubes display an electroconductive network. In the effective system, tungsten carbide particles cracks due to mechanical stress during the growth of carbon nanotubes but the fragments still connect to the carbon nanotubes. It provides both conductive network and numerous active sites for the ideal electrocatalysts. Finally the tungsten carbide-carbon nanotubes are evaluated as an alternative catalyst for methanol oxidation reaction after being platinized. The peak current density of optimized sample reaches 1350 mA mg-1 Pt which is more than twice that of commercial Platinum Carbon.

Design of Materials for Electroreduction of Nitrogen to Ammonia: A Computational Perspective

Theoretical studies and computational modeling play a key role in predicting various properties of catalytic materials, including their activity and selectivity towards a desired electro-catalytic pathway. In the last decade, density functional theory calculations have been used to study the activity and selectivity of various materials for the nitrogen electroreduction, an extremely important aspect in the development of novel technologies for the ammonia synthesis. However, the design of an ideal electro-catalyst that exhibits high activity for nitrogen reduction to ammonia while at the same time suppresses the competing hydrogen evolution reaction is still an ongoing pursuit. Here we will use the example of molybdenum nitride and molybdenum carbide to illustrate different aspects in the design of materials for nitrogen electroreduction to ammonia and discuss different challenges associated with this effort [1, 2]. We will first present calculations of free energy diagrams and kinetic volcano plots aimed at understanding the activity of different surfaces of the molybdenum nitride (Mo2N) and molybdenum carbides (MoC and Mo2C) towards hydrogen evolution reaction and nitrogen electroreduction to ammonia. Secondly, we will discuss the thermodynamics calculations directed towards understanding the stability of these materials at different cell potentials and pH. Namely, our results show that at the nitrogen reduction potentials the catalytic surface can be covered with the H-adatoms rather than the N-adatoms. In addition, the carbides and nitrides can be converted to oxynitrides or oxides, which can lead to the decrease in the activity and durability of the catalytic material. Molybdenum carbides and nitrides will be used to illustrate how computational modeling can direct the design of the active sites with highest efficiency for nitrogen reduction to ammonia, but also support the optimization of reaction conditions to ensure the catalyst durability. [1] I. Matanovic, F. H. Garzon, and N. J. Henson, Electro-reduction of Nitrogen on Molybdenum Nitride: Structure, Energetics, and Vibrational Spectra from DFT, Phys. Chem. Chem. Phys. 2014, 16: 3014-3026. [2] I. Matanovic and F. H. Garzon, Nitrogen Electroreduction and Hydrogen Evolution on Cubic Molybdenum Carbide: A Density Functional Study, Phys. Chem. Chem. Phys. 2018, 20: 14679-14687.

Engineering multiphase for activating electroactive sites for highly efficient hydrogen evolution: Experimental and theoretical investigation

Abstract An ideal electrocatalyst for the hydrogen evolution reaction of water splitting requires substantial active sites with high catalytic activity, fast electron and mass transfer, low gas adsorption energy, and high stability. However, a single component catalyst usually has only one of the many properties of an ideal electrocatalyst. Herein, for the first time, we synthesize CoxSe/MoSe2 micro-prisms on foam via a hydrothermal and selenization strategy. After selenization, a crystallized CoMoO4 smooth prismatic structure can be converted into a CoxSe/MoSe2 prismatic structure with lamellar morphology. Such synergistic effects lead to CoxSe/MoSe2 superior electrochemical catalytic activity with a 109 mV over-potential at 10 mA cm−2 and 204 mV over-potential at 100 mA cm−2, an appropriate Tafel slope of 90 mV dec−1, and remarkable long-term stability during 20 h of testing for the hydrogen evolution reaction in an alkaline medium. Density-functional calculations reveal the absorption energy of water and Gibbs free-energy of intermediate adsorb hydrogen of CoxSe/MoSe2 is more favorable for hydrogen evolution reaction than single component catalyst. Both experimental and theoretical calculation results reveal that synergistic effect can efficiently reduce energy barrier of both the initial water adsorption step and subsequent H2 generation on binary catalysts, and improve catalytic activity.

Fe-Doping in Double Perovskite PrBaCo2(1-x)Fe2xO6-δ: Insights into Structural and Electronic Effects to Enhance Oxygen Evolution Catalyst Stability

Perovskite oxides have been gaining attention for its capability to be designed as an ideal electrocatalyst for oxygen evolution reaction (OER). Among promising candidates, the layered double perovskite—PrBaCo2O6-δ (PBC)—has been identified as the most active perovskite electrocatalyst for OER in alkaline media. For a single transition metal oxide catalyst, the addition of Fe enhances its electrocatalytic performance towards OER. To understand the role of Fe, herein, Fe is incorporated in PBC in different ratios, which yielded PrBaCo2(1-x)Fe2xCo6-δ (x = 0, 0.2 and 0.5). Fe-doped PBCF’s demonstrate enhanced OER activities and stabilities. Operando X-ray absorption spectroscopy (XAS) revealed that Co is more stable in a lower oxidation state upon Fe incorporation by establishing charge stability. Hence, the degradation of Co is inhibited such that the perovskite structure is prolonged under the OER conditions, which allows it to serve as a platform for the oxy(hydroxide) layer formation. Overall, our findings underline synergetic effects of incorporating Fe into Co-based layered double perovskite in achieving a higher activity and stability during oxygen evolution reaction.

NiFe-based nanostructures on nickel foam as highly efficiently electrocatalysts for oxygen and hydrogen evolution reactions

Abstract Water splitting, as an advanced energy conversion technology, consists of two half reactions, including oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). However, the ideal electrocatalysts are noble metal based catalysts. Their high cost and scarcity in earth seriously restrict the large deployments. NiFe-based materials have attracted great attention in recent years due to their excellent catalytic properties for OER and HER. Nevertheless, their conductivity and electrochemical stability at high current density are unsatisfactory, resulting in ineffective water splitting due to high impedance and low stability. Recently, a series of catalysts coating NiFe-based materials on 3D nickel foam were found to be extremely stable under the circumstance of high current density. In this review, we summarized the recent advances of NiFe-based materials on nickel foam for OER and HER, respectively, and further provided the perspectives for their future development.

Long-Life Rechargeable Zn Air Battery Based on Binary Metal Carbide Armored by Nitrogen-Doped Carbon

Developing low-cost and high-performance bifunctional oxygen electrocatalysts is essential for commercial realization of regenerative fuel cells and rechargeable metal air batteries. Iron carbide (Fe3C) is an ideal electrocatalyst candidate; however, its poor oxygen evolution reaction (OER) activity and stability make it serve only as a unifunctional oxygen reduction reaction (ORR) electrocatalyst. Here, we report a robust bifunctional electrocatalyst consisting of manganese–iron binary carbide (MnxFe3–xC) nanoparticles armored by nitrogen-doped graphitic carbon (MnxFe3–xC/NC). Synthesis involved facile pyrolysis of a trimetallic (Fe, Mn, Zn) zeolitic imidazolate framework. Incorporation of Mn modulated the electronic properties of Fe3C and the surrounding carbon, enhancing ORR and OER activities. MnxFe3–xC, well-armored by carbon layers, displayed high resistance to oxidation and corrosion. The assembled Zn-air battery (ZAB) exhibited a large peak power density (160 mW cm–2 at 250 mA cm–2) with an energy...

Grafting Poly(acrylic acid) from PEDOT To Control the Deposition and Growth of Platinum Nanoparticles for Enhanced Electrocatalytic Hydrogen Evolution

Electrochemical water splitting is a sustainable, environmentally friendly method of hydrogen generation for green energy. However, the ideal electrocatalyst, platinum, is limited by cost and scarcity. Thus, new approaches are needed to minimize the amount of platinum required for efficient hydrogen production, while its electrocatalytic activity is retained. In this work, we report the development of a novel electrocatalyst based on platinum nanoparticles (PtNPs) deposited on conducting poly(3,4-ethylenedioxythiophene) (PEDOT), grafted with poly(acrylic acid) (PAA) chains. The presence of PAA controls the PtNP size and prevents aggregation during electrodeposition. The composite materials demonstrated enhanced electrocatalytic activity for the hydrogen evolution reaction (HER) in acid, with onset potentials as low as −84 mV vs RHE and exchange current densities up to 161 μA cm–2. Thus, these composite electrodes show promise as a straightforward, cost-effective alternative to conventional platinum HER ca...

Highly active and stable electrocatalysts of FeS2–reduced graphene oxide for hydrogen evolution

Electrocatalytic hydrogen evolution is the most cost-effective method for producing hydrogen as a large-scale clean energy source. Thus, catalysts of low-cost hydrogen evolution are developing at great speed. FeS2–reduced graphene oxide (RGO) hybrid catalysts are synthesized with the use of abundant and inexpensive component worldwide. The catalyst has satisfactory electrocatalytic performance and excellent stability in 0.5 M H2SO4 solution. The catalyst supported by RGO is the ideal electrocatalyst with satisfactory electrical conductivity with 61 mV dec−1 of the Tafel slope. What is more, the current density changes slightly in 36 h and the catalytic performance is relatively stable at 200 mV overpotential. Therefore, the catalyst supported by RGO has high potential for industrial production due to its simple composition and satisfactory electrocatalytic effect.

Designing Cathode Layers for PEFC with the Low Platinum-Loading

Introduction Since the reduction of platinum-loadings in polymer electrolyte fuel cells (PEFCs) is essential for the further spread of their technology, many researchers have been working on this subject. Among those studies, the importance of controlling and optimizing structures of catalyst layers including the carbon frame has been reported for designing highly efficient PEFC with the low platinum-loading.1 In this study, membrane electrode assemblies (MEAs) with various platinum-loadings in the cathode are made and evaluated as a fundamental approach to reduce the platinum-loading. Then, we are trying to understand minimum requirement of platinum and to correlate resulting overvoltages with structures of cathode layers, and we are accordingly aiming to design highly efficient PEFC with the low platinum-loading. Experimental MEAs with various platinum-loadings in the cathode were prepared with 46% Pt deposited Ketjen black (TEC10E50E) and Nafion® by a spray printing method.2 Then, MEAs were evaluated in terms of impedance, IV performance, and ECSA. The thickness of catalyst layers were also measured by FIB-SEM. For further designing ideal electrocatalysts, electrocatalysts with different amounts of Pt deposition were made using Vulcan carbon as a carbon support and platinum(II) acetylacetonate as a platinum precursor through thermal reduction.3 Results and discussion MEAs with the fixed anode (0.30 mgPt/cm2) and the varied cathodes (0.05 – 0.40 mgPt/cm2) have been prepared and evaluated in our study. Then, the minimum requirement of platinum in the cathode has been determined to 0.15 – 0.20 mgPt/cm2 through correlating the platinum-loading with activation overvoltage. Furthermore, the requirement of sufficient thickness of cathode layers has been found for reducing concentration overvoltage.4 In this report, the correlation between carbon amounts and concentration overvoltage was further evaluated by preparing MEAs with 0.05 – 0.60 mgPt/cm2 cathodes. Since decrease in the gas diffusion pathway by decreasing the cathode layer also leads to increase in the concentration of water produced by fuel cell reactions in the cathode layer, there should be the optimum thickness in terms of sufficient fuel diffusion. As a result, the optimum thickness was found to be 8.24 µm in this study. Since the importance of cathode thickness was realized for designing PEFC with the low platinum-loading, electrocatalysts with reduced Pt deposition on carbon were prepared in order to increase the cathode thickness even with reduced platinum-loadings. Consequently, successful reduction of concentration overvoltage was suggested from our experimental results. Obtained results will be explained more in details. (1) M. Lee, et al., Electrochimica Acta, 56 (2011) 4783-4790. (2) M. Okumura, et al., J. Electrochem. Soc., 164 (9), F928 (2017). (3) A. Hayashi, et al., Electrochemica Acta, 53, 6117 (2008). (4) K. Uda, et al., ECS Trans., 80 (8), 789 (2017). Figure 1

Investigation of Pd and Pd-CeO2 Based Carbon-Supported Electrocatalysts for the Electrooxidation of Borohydride in Direct Borohydride Fuel Cell

Direct borohydride fuel cells (DBFC) are considered high-energy density generators. The ideal case for the anodic reaction of a DBFC is the direct and complete borohydride oxidation reaction (BOR) that releases 8 electrons. However, the BOR is a very complex reaction that involves numerous intermediate species and suffers from competition with the heterogeneous hydrolysis of BH4 - that leads to molecular hydrogen, making full utilization of the fuel challenging [1]. Despite many studies of the BOR on several electrocatalysts (especially Au and Pt), this reaction is still poorly understood on most practical electrocatalysts and in relevant conditions to DBFC operation, and no ideal electrocatalyst fulfilling both high activity and high faradaic efficiency at low potential has been isolated, yet. In this study, the BOR is investigated on Pd-based carbon-supported electrocatalysts. A set of four Pd/C electrocatalysts have been synthesized using Vulcan XC72 as substrate and loaded at 22, 33, 44 and 53 wt% Pd. These materials have been thoroughly characterized in terms of BOR activity in a rotating disk electrode setup. The experiments were performed for three NaBH4 concentrations (5, 50 and 500 mM) at 60°C. The electrochemical characterizations of Figure 1 (A) reveal that the onset potential (E i=0) (see Figure 1 (B)) is lower than 0 V vs. RHE on all the Pd electrocatalysts, meaning that BH4 - anions can be valorized directly, albeit with slow kinetics. In contrast, Pt/C first decomposes BH4 - and utilizes hydrogen species, above 0 V vs. RHE. However, the kinetic is very slow. Similar experiments have been performed with advanced Pd electrocatalysts with a composite support made of Vulcan XC72 carbon and cerium oxide, which enhance hydrogen oxidation reaction (HOR) kinetics in alkaline media [2]. Figure 1

Facile Synthesis of Ni-Based Catalysts by Adsorption and Conversion of Metal Ions on Graphene Oxide for Methanol Oxidation

Controllable synthesis of highly dispersed non-precious nanocatalysts is an attractive strategy to prepare efficient electrocatalysts for fuel cell applications. In this study, a facile synthesis of Ni-based mono- and bimetallic nanocatalysts has been developed by adsorption and conversion of metal ions on graphene oxide. The morphology and composition of Ni catalyst are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The electrochemical and electrocatalytic properties of Ni catalysts are studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopic techniques. The catalytic performance can be improved easily by increasing the adsorption and deposition cycles of metal ions and changing the composition of precursor metal ions solution. This work will be of general interest to design efficient nanostructured catalysts and find ideal electrocatalysts for application with high catalytic performance and low price.

Engineering NiMo3S4|Ni3S2 interface for excellent hydrogen evolution reaction in alkaline medium

Ideal electrocatalyst for hydrogen evolution reaction demands abundant reactive centers with high activity, fast electron and mass transfer, unhindered release of gas bubbles and long-term operation stability. Engineering different components' interface of the composite catalyst can lead to significantly enhanced performance. In this study, excellent activity of NiMo3S4|Ni3S2 seamlessly grown on 3D conductive framework has been demonstrated. Two-step approach has been adopted to synthesize the final catalyst via subsequently reacting (NH4)2MoS4 with Ni(OH)2 nanosheets array hydrothermally grown on nickel foam. As compared to the MoS2|Ni3S2 obtained by directly reacting (NH4)2MoS4 with the nickel foam, NiMo3S4|Ni3S2 demonstrates much superior behavior in terms of current density and Tafel value. On basis of the data analysis, the variance of electrochemical surface area (ECSA) and electron transfer resistance are not the key descriptor for performance of the electrocatalyst in this study. It is considered that the new formed interface between NiMo3S4|Ni3S2 contributes significantly to the boosted activity. Such nanostructured architecture shows promising results for hydrogen evolution reaction in alkaline medium with only 23.4 mV overpotential for the current density of 10 mA cm−2 and robust long-term stability during more than 20 h test.