Interface engineering of the NiCo2O4@MoS2/TM heterostructure to realize the efficient alkaline oxygen evolution reaction

Electrochemical water splitting is considered as a promising strategy for the efficient hydrogen production, yet it is hindered by the sluggish oxygen evolution reaction (OER). Herein, heterostructure OER catalyst is fabricated by combining MoS₂ nanosheets with NiCo₂O₄ hollow sphere on Ti mesh. Benefiting from the heterogeneous nanointerface between NiCo₂O₄ and MoS₂, this electrocatalyst demonstrates excellent OER activity in basic environment with overpotentials of 313 and 380 mV achieving 10 and 100 mA cm⁻². The superb catalytic performance stems from hollow the nanostructure and interfacial engineering strategy that enhance intrinsic activity and provide faster charge transfer. Hence, this work provides a feasible path for exploiting the high-efficient catalysts.     

Facile synthesis of three-dimensional spherical Ni(OH)2/NiCo2O4 heterojunctions as efficient bifunctional electrocatalysts for water splitting

Synthesis of highly efficient, non-noble and bi-functional electrocatalysts is exceedingly challenging and necessary for water splitting devices. In this work, three-dimensional spherical Ni(OH)₂/NiCo₂O₄ heterojunctions are prepared by a one-step hydrothermal method and the hybrids are explored as efficient electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in an alkaline electrolyte via tuning different Ni/Co atomic ratios of heterojunctions. The optimized Ni(OH)₂/NiCo₂O₄ (S (1:1)) exhibits high electrocatalytic activity with an ultralow over-potential of 189 mV at 10 mA cm⁻² for the HER. With regard to the OER, the over-potential of the as-synthesized S (1:1) heterojunction is only 224 mV at the current density of 10 mA cm⁻². The improved catalytic performance of the Ni(OH)₂/NiCo₂O₄ heterojunctions is attributed to the chemical synergic combining of Ni(OH)₂ and NiCo₂O₄, large specific surface area for exposing more accessible active sites, and heterointerface for activating the intermediates that facilitates electron/electrolyte transport. The prepared catalyst exhibits good durability and stability in HER and OER catalyzing conditions. This study provides a feasible approach for the building of highly efficient bifunctional water splitting electrocatalysts and stimulates the development of renewable energy conversion and storage devices.     

NiCoP coated on NiCo2S4 nanoarrays as electrode materials for hydrogen evolution reaction

It is very important to exploit robust electrocatalysts for the urea splitting in an alkaline medium. Hence, the NiCo₂S₄@NiCoP nanoarrays on Ni foam (NiCo₂S₄@NiCoP/NF) was successfully synthesized for the first time and used as an efficient and stable difunctional electrocatalyst for the overall urea splitting. As one of the most promising bifunctional electrocatalysts reported, NiCo₂S₄@NiCoP only needs 108 mV to reach current density of 10 mA cm⁻² for hydrogen evolution reaction. Moreover, such NiCo₂S₄@NiCoP//NiCo₂S₄@NiCoP electrodes couple display superior urea splitting performance with the requirement of a cell voltage of 1.53 V to drive a catalytic current density of 10 mA cm⁻². In addition, the NiCo₂S₄@NiCoP material presents high long-term electrocatalytic stability keeping its performance at 11 mA cm⁻² for 12 h. The experimental results demonstrate that the sluggish Volmer step has been improved by incorporating the NiCoP to the NiCo₂S₄.     

Construction of NiCo2S4/Ni3S2 nanoarrays on Ni foam substrate as an enhanced electrode for hydrogen evolution reaction and supercapacitors

Developing a multifunctional and sustainable electrode material for hydrogen evolution reaction and supercapacitors is a highly feasible avenue for producing the high energy density and renewable energies. In our study, nanostructured NiCo₂S₄/Ni₃S₂/NF nanoarrays are rational developed in experiments via a simple hydrothermal reaction. Ascribed to the 3D nanostructured NiCo₂S₄/Ni₃S₂ with numerous exposure active sites and large contact areas for the electrolyte, the binder-free feature of NiCo₂S₄/Ni₃S₂/NF facilitates a low charge transfer resistance, as well as the synergetic effect of NiCo₂S₄ and Ni₃S₂. The obtained electrocatalyst showed ultrahigh electrocatalytic activity with an overpotential of 111 mV at 10 mA cm⁻² and a Tafel slope of 57 mV dec⁻¹. In addition, the electrode showed an area specific capacity of 6.13 F cm⁻² at 10 mA cm⁻² and superior rate capability (2.72 F cm⁻² at 80 mA cm⁻²), accompanied by excellent cycling stability. This results presented in our work can provide an effective strategy for rational design of other hybrid materials with excellent electrochemical performance in the application of electrocatalysis and supercapacitors.     

Fe-doped NiCo2S4 catalyst derived from ZIF – 67 towards efficient hydrogen evolution reaction

The development of economical, efficient and stable non-noble metal catalysts plays a key role in electrocatalytic hydrogen evolution. NiCo₂S₄ has been proved to be an efficient non-noble catalyst, to further improve its electrocatalytic performance is a meaningful work. In this paper, the effects of Fe doping on electrochemical performance of NiCo₂S₄ is investigated. The Fe-doped NiCo₂S₄ catalyst is prepared by a facile solvothermal method with metal-organic-framework (MOF, ZIF-67) as template, and it exhibits an improved hydrogen evolution reaction (HER) performance with an overpotential of 181 mV at 10 mA cm^?2, a Tafel slope of 125 mV dec^?1 compared with that of NiCo₂S₄ (252 mV overpotential and 149 mV dec^?1 Tafel slope). The combination of improved conductivity, mesopores architecture retained with the ZIF-67 template, which result the reduced internal resistance, enhanced charge transportation as well as large electrochemical double-layer capacitance. This work provides an effective and synergistic strategy for fabricating NiCo₂S₄-based catalysts toward electrochemical water splitting.     

Co,N co-doped carbon nanosheets coupled with NiCo2O4 as an efficient bifunctional oxygen catalyst for Zn-air batteries

Developing of inexpensive and efficient bifunctional oxygen catalysts is important for the zinc-air batteries (ZABs). Here, a composite of Co, N co-doped carbon nanosheets coupled with NiCo₂O₄ (NiCo₂O₄/CoNC-NS) is developed as oxygen catalyst, which has good bifunctional oxygen catalytic activity and durability. Specifically, the half-wave potential of oxygen reduction reactions (ORR) is 0.849 V, and the overpotential of oxygen evolution reactions (OER) is 1.582 V at a current density of 10 mA cm⁻². And the assembled liquid ZABs based on NiCo₂O₄/CoNC-NS exhibit high open circuit potential (OCP, 1.482 V), high peak power density (148.3 mW cm⁻²) and large specific capacity (699.9 mAh g⁻¹) with long-term stability. Moreover, the further assembled solid ZABs can also provide high OCP (1.401 V), good power density (58.1 mW cm⁻²) and superior stability. This work would provide a good reference for the development of other advanced oxygen catalyst in future.     

Metal tungstate dominated NiCo2O4@NiWO4 nanorods arrays as an efficient electrocatalyst for water splitting

One of the most promising ways to produce high purity hydrogen is electrocatalytic water splitting, the slow rate of oxygen evolution reaction (OER) limited the whole water splitting process under alkaline conditions. Here, NiCo₂O₄@NiWO₄/NF is firstly acted as a metal tungstate dominated bifunctional water splitting catalyst, which a very low cell voltage of 1.59 V is obtained with 10 mA cm⁻² in alkaline media. Remarkably, the catalytic performance of NiCo₂O₄@NiWO₄/NF is also kept for at least 12 h, which shows long time electrochemical stability.     

Facile construction of well-defined hierarchical NiFe2O4/NiFe layered double hydroxides with a built-in electric field for accelerating water splitting at the high current density

Interfacial charge redistribution induced by a strong built-in electric field can expertly optimize the adsorption energy of hydrogen and hydroxide for improving the catalytic activity. Herein, we develop a well-defined hierarchical NiFe₂O₄/NiFe layered double hydroxides (NFO/NiFe LDH) catalysts, exhibiting superior performance due to the strong interfacial electric field interaction between NiFe₂O₄ nanoparticle layers and NiFe LDH nanosheets. In 1 M KOH, NFO/NiFe LDH needs 251 mV and 130 to drive 50 and 10 mA cm^?2 for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Moreover, only 1.517 V cell voltage is needed to reach 10 mA cm^?2 towards overall water splitting. Notably, under simulated industrial electrolysis conditions, NFO/NiFe LDH only needs 289 mV to drive 1000 mA cm^?2. This work puts a deep insight into the role of the built-in electric field in transition metal-based catalysts for accelerating water splitting and scalable industrial electrolysis applications.     

Advanced catalysts for hydrogen evolution reaction based on MoS2/NiCo2S4 heterostructures in Alkaline Media

There are great challenges to develop and fabricate a high performance, low-cost and stable non-platinum catalyst for hydrogen evolution reaction (HER). In our study, we firstly developed a simple method to successfully fabricate a new MoS₂/NiCo₂S₄ heterostructure by a two-step hydrothermal method, and studied the HER property of MoS₂/NiCo₂S₄, where the as-prepared NiCo-layered double hydroxide (NiCo-LDH) was used as the precursor of NiCo₂S₄. Benefitting from the prominent synergistic effect between NiCo₂S₄ and MoS₂, MoS₂ provided massive catalytic active edge sites, and NiCo₂S₄ enhanced the conductivity of the composite. As a result, the MoS₂/NiCo₂S₄ showed excellent HER catalytic activity, with a current of 10 mA cm⁻² at overpotential of 94 mV for HER and a low Tafel slope of 46 mV dec⁻¹, and good cycling stability in Alkaline Media. As well as, our work offered one promising high active and stable non-platinum catalyst for overall water splitting.     

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

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 Co_xSe/MoSe₂ micro-prisms on foam via a hydrothermal and selenization strategy. After selenization, a crystallized CoMoO₄ smooth prismatic structure can be converted into a Co_xSe/MoSe₂ prismatic structure with lamellar morphology. Such synergistic effects lead to Co_xSe/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 Co_xSe/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.     

High-performance bifunctional Fe-doped molybdenum oxide-based electrocatalysts with in situ grown epitaxial heterojunctions for overall water splitting

The design and development of low-cost, abundant reserves, high catalytic activity and durability bifunctional electrocatalysts for water splitting are of great significance. Here, simple hydrothermal and hydrogen reduction methods were used to fabricate a uniform distribution of Fe-doped MoO₂/MoO₃ sheets with abundant oxygen vacancies and heterojunctions on etched nickel foam (ENF). The Fe– MoO₂/MoO₃/ENF exhibited a small overpotential of 36 mV at 10 mA cm⁻² for hydrogen evolution reaction (HER), an excellent oxygen evolution reaction (OER) overpotential of 310 mV at 100 mA cm⁻² and outstanding stabilities of 95 h and 120 h for the HER and OER, respectively. As both cathode and anode catalysts, the heterogeneously structured Fe– MoO₂/MoO₃/ENF required a low cell voltage of 1.57 V at 10 mA cm⁻². Density functional theory (DFT) calculations show that Fe doping and MoO₂/MoO₃ heterojunctions can significantly reduce the band gap of the electrode, accelerate electron transport and reduce the potential barrier for water splitting. This work provides a new approach for designing metal ion doping and heterostructure formation that may be adapted to transition metal oxides for water splitting.     

Facile synthesis of highly active monolithic water-separated W-doped Ni–Fe–P catalysts

A new type of highly active and cost-effective nanoporous W-doped Ni–Fe–P catalyst on nickel foam (NF) was synthesized by a facile electroless plating method. The W-doped Ni–Fe–P/NF catalysts exhibit extraordinary catalytic activity for hydrogen evolution reaction (HER) in alkaline media, capable of yielding a current density of −10 mA cm⁻² at an overpotential of only 68 mV. Furthermore, the catalysts also show efficient activity towards oxygen evolution reaction (OER) with an overpotential of 210 mV at j = 10 mA cm⁻² as well. The W-doped Ni–Fe–P/NF electrocatalyst exhibits a long-term durability over 13 h test.     

Flower-shaped and sea urchin-shaped structures coexisting in cobalt-based phosphate and oxides achieve efficient electrochemical overall water electrolysis

Active site engineering for electrocatalysts is an essential strategy to improve their intrinsic electrocatalytic capability for practical applications and it is of great significance to develop a new excellent electrocatalyst for overall water splitting. Here, Co₃O₄/nickel foam (NF) and Co₂(P₄O₁₂)/NF electrocatalysts with flower-shaped and sea urchin-shaped structures are synthesized by a simple hydrothermal process and followed by a post-treatment method. Among them, Co₂(P₄O₁₂)/NF shows good catalytic activity for hydrogen evolution reaction (HER), and at the current density of 10 mA cm^?2, the overpotential is only 113 mV Co₃O₄/NF exhibits good catalytic activity for oxygen evolution reaction (OER), and the overpotential is 327 mV at 20 mA cm^?2. An alkaline electrolyzer with Co₃O₄/NF and Co₂(P₄O₁₂)/NF catalysts respectively as anode and cathode displays a current density of 10 mA cm^?2 at a cell voltage of 1.59 V. This work provides a simple way to prepare high efficient, low cost and rich in content promising electrocatalysts for overall water splitting.     

Ru nanoclusters coupling with hierarchical phosphorus and oxygen dual-doped carbon nanotube architectures for effective hydrogen evolution reaction

The construction of an effective catalyst for hydrogen evolution reaction (HER) is a top priority. Herein, we demonstrate ruthenium (Ru) nanoclusters coupled with phosphorus and oxygen dual-doped carbon nanotube (CNT) architecture (Ru-POCA). The increased hydrophilicity and negatively charged surface of CNTs can strongly trap Ru ions. The hierarchical structure is favorable of providing abundant pathways and exposing more active sites for HER. Due to the synergistic effect of the hierarchical structure and modified surface chemistry, Ru-POCA exhibits excellent catalytic HER activity. The overpotential is 22 and 40 mV with a Tafel slope of 28.0 and 27.1 mV dec⁻¹ in 1 M KOH and 0.5 M H₂SO₄ at 10 mA cm⁻². Moreover, Ru-POCA processes good catalytic stability in both acidic and alkaline electrolytes, while the boosted catalytic HER activity is fundamentally studied by density functional theory calculation. This work provides a rational approach to constructing hierarchically structured Ru-CNTs-based catalysts for hydrogen evolution reaction.     

CoO/NF nanowires promote hydrogen and oxygen production for overall water splitting in alkaline media

The exploration of catalysts with high activity and low cost for water splitting is still necessary. Herein, a nanowire-like morphology CoO/NF electrode is synthesized using facile hydrothermal reaction and calcination treatment. The urea can regulate its morphology during the synthetic process of CoO/NF. Electrochemical studies reveal that the as-obtained CoO/NF exhibits excellent electrocatalytic performance with overpotential of 307 mV at current density of 10 mA cm⁻² and Tafel slope of 72 mV dec⁻¹ for oxygen evolution reaction, and CoO/NF delivers current density of 10 mA cm⁻² at overpotential of 224 mV for hydrogen evolution reaction. The results of the oxygen evolution reaction stability show that the overpotential of CoO/NF electrode is only increased by 4 mV at current density of 10 mA cm⁻². The two-electrode water splitting with CoO/NF electrodes as both anode and cathode needs a cell potential of 1.76 V to reach 10 mA cm⁻². Therefore, this simple method to prepare CoO/NF electrode can enhance the properties of electrocatalysts, which makes CoO/NF a promising material to replace noble metal-based catalysts.     

Spinel NiCo2O4 3-D nanoflowers supported on graphene nanosheets as efficient electrocatalyst for oxygen evolution reaction

Efficient oxygen evolution reaction (OER) electrocatalysts with non-noble metals are very critical for the large-scale exploitation of electrocatalytic hydrogen production systems. To improve the catalytic activity of OER electrocatalysts, several design strategies, such as construction of nanostructures, porous structures and composite materials have been proposed. Herein, spinel NiCo₂O₄ 3-D nanoflowers supported on graphene nanosheets (GNs) are prepared by a simple solvothermal synthesis method as non-noble metal electrocatalysts for OER. The present NiCo₂O₄/GNs composite integrates multiple advantages of nanostructures, porous structures and composite materials, including high surface area, abundant catalytic sites and high stability. Benefiting from the favorable features, the NiCo₂O₄/GNs composite exhibits a better OER performance than NiCo₂O₄ and RuO₂ in alkaline medium, which has a low onset potential (1.50 V), a small Tafel slope (137 mV dec⁻¹). The present work opens a new window for the construction of the carbon-supported 3-D nanostructure of transition metal catalysts with optimizable electrocatalytic performances for electrocatalytic hydrogen production.     

Construction of NiFeP/CoP nanosheets/nanowires hierarchical array as advanced electrocatalysts for water oxidation

Cost-effective hierarchical electrocatalysts with excellent performance and high stability for water splitting play an important role in promoting social sustainable development. Herein, we report a three-dimensional (3D) trimetallic nickel-iron-cobalt phosphide with a hierarchical nanoarray structure grown in situ on carbon cloth via a combined method of two-step hydrothermal reaction and following low-temperature phosphating using a carbon cloth as a conductive substrate. The synthesized NiFeP/CoP/CC exhibits excellent oxygen evolution reaction (OER) catalytic performance, giving small overpotentials of 250 mV, 270 mV and 320 mV at current densities of 20 mA cm⁻², 50 mA cm⁻² and 200 mA cm⁻² in alkaline electrolyte, respectively, with a small Tafel slope of 51 mV dec⁻¹. In addition, the catalytic activity of the material remains stable for at least 50 h, and the turnover frequency (TOF) is 0.466 mol O₂ s⁻¹ at an over potential of 300 mV. These properties of the material are comparable to those of the noble metal catalyst RuO₂/CC, which may be ascribed to the hierarchical microstructure, good conductivity and desirable synergistic effect among metal ions.     

CoSe2@NiSe2 nanoarray as better and efficient electrocatalyst for overall water splitting

Electrocatalytic water splitting is identified as one of the most promising solutions to energy crisis. The CoSe₂@NiSe₂ materials were first prepared and in situ grown on nickel foam by typical hydrothermal and selenification process at 120 °C. The results show that the CoSe₂@NiSe₂ material used as the 3D substrates electrode can maximize the synergy between the CoSe₂ and NiSe₂, and also exhibits high efficiency of water splitting reaction. The lower overpotential of only 235 mV is presented to attain 20 mA cm⁻² compared to the benchmark of RuO₂ electrodes (270 mV @ 20 mA cm⁻²). Besides, the CoSe₂@NiSe₂ material also shows a remarkable improved hydrogen evolution reaction activity compared to NiSe₂ (192 mV@10 mA cm⁻²) and Co precursor catalysts (208 mV@10 mA cm⁻²) individually, which a low overpotential of only 162 mV is achieved at 10 mA cm⁻². The CoSe₂@NiSe₂ catalysts exhibit excellent water splitting performance (cell voltage of 1.50 V@ 10 mA cm⁻²) under alkaline conditions. It was proved that the high water splitting performance of the catalyst is attributed to high electrochemical activity area and synergistic effect. The work offers new ideas for the exploitation of synergistic catalysis of composite catalysts and adds new examples for the exploitation of efficient, better and relatively non-toxic electrocatalysts.     

Cobalt-molybdenum disulfide supported on nitrogen-doped graphene towards an efficient hydrogen evolution reaction

Herein, the cobalt-molybdenum bimetallic sulfide catalysts supported on nitrogen-doped graphene (CoMoS₂/NGO) were facilely synthesized by a one-pot hydrothermal route. These composites exhibit various special nanostructures, rich in abundant edge site exposure and defects, which play an important role in providing active sites for catalyzing hydrogen evolution reaction (HER). When hydrogen peroxide (H₂O₂) was used as an additive in hydrothermal process, the as-fabricated composite exhibited more efficiency towards HER, showing as low onset overpotential (η_on) as −54 mV in 0.5 M H₂SO₄. Typical H₂O₂-assisted composite realized a remarkable cathodic current density of 30 mA cm⁻² at an overpotential η = −137 mV and it possessed a small Tafel slope of 34.13 mV dec⁻¹. Moreover, it exhibited an excellent cycling stability and superior electronic exchange rate. The results prove that CoMoS₂/NGO catalysts have great potential for electrochemical HER.     

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.