Controllable transformation of sheet-like CoMo-hydro(oxide) and phosphide arrays on nickel foam as efficient catalysts for alkali water splitting and Zn–H2O cell

Design and synthesis of cost-effective electrocatalysts with remarkable activity and stability is highly desirable for renewable energy devices. Herein, we have successfully constructed sheet-like CoMoO₄–Co(OH)₂ and CoMoP–CoP arrays on nickel foam (NF) through chemical etching ZIF-67 arrays and phosphorization in sequence. Series CoMoO₄–Co(OH)₂/NF as anode and CoMoP–CoP/NF as cathode showed excellent electrocatalytic activity and stability in alkali water splitting, where the combined catalysts only need 1.67 V cell voltage to drive 10 mA cm^?2 and obtain robust high current stability at 500 mA cm^?2 for 110 h with almost no attenuation. In addition, using CoMoP–CoP/NF as the cathode of a Zn–H₂O cell can provide a power density of 11.5 mW cm^?2 and a stable 170 h for simultaneous H₂ and electricity generation. The excellent performance of the system is attributed to the unique sheet-like array morphology of combined catalysts providing large surface area and rich pore structure conducive to electrolyte diffusion and gas emission, as well as the synergies between the different components providing more catalytic active sites.     

Electrodeposited Ni–Co–S nanosheets on nickel foam as bioelectrochemical cathodes for efficient H2 evolution

High overpotential and soaring prices of the cathode electrode are the bottlenecks for the development of microbial electrolysis technology for hydrogen production. In this study, a novel one-step electrodeposition method has been attempted to fabricate electrodeposited cathodes in situ growth of Ni–Co–S, Ni–S, Co–S catalyst on nickel foam (NF) to reduce the overpotential of electrodes. Finally, a uniform nanosheet with a high specific surface area and more active sites is formed on the NF surface, resulting in a lower overpotential than plain NF. At 0.8 V, the Co–S/NF cathode produces a favorable 42% increase in hydrogen yield (0.68 m³·m⁻³·d⁻¹), 40% upsurge in current density (10.6 mA/cm³) and 39% rise of cathodic recovery rate (58.0 ± 3.2%) than bare NF, followed by Ni–Co–S/NF and Ni–S/NF cathode. All the electrodeposited electrodes demonstrate enhanced current density and reduced electron losses, thereby achieving efficient hydrogen production. These innovative varieties of electrodes are highly advantageous as they are relatively inexpensive and easy to manufacture with great potential in reducing costs and further real time application in large scale.     

Vermicular Ni3S2–Ni(OH)2 heterostructure supported on nickel foam as efficient electrocatalyst for hydrogen evolution reaction in alkaline solution

Alkaline solution is considered to be more suitable for industrial application of hydrogen production by water electrolysis. However, most of the low-cost electrocatalyts such as Ni₃S₂ has poor ability to dissociate HO–H, resulting in unsatisfied hydrogen evolution performance in alkaline media. In this paper, a novel vermicular structure of Ni₃S₂–Ni(OH)₂ hybrid have been successfully prepared on nickel foam substrate (v-Ni₃S₂–Ni(OH)₂/NF) through a facile two-step containing hydrothermal and electrodeposition processes. The heterostructure consists of rod-like Ni₃S₂ and Ni(OH)₂ nanosheets, in which Ni(OH)₂ is coated on the surface of Ni₃S₂. This structure not only constructs a fast electron transfer channel but also possesses rich heterointerface, thus accelerating the Volmer step and allowing more active sites of Ni₃S₂ to functioning well. As a result, v-Ni₃S₂–Ni(OH)₂/NF exhibited excellent electrocatalytic activity toward HER in 1.0 M KOH solution. It only needs 78 mV and 137 mV to drive current density of 10 mA cm⁻² and 100 mA cm⁻². Moreover, the catalytic stability of this electrocatalyst in alkaline solution is also satisfactory.     

Three-dimensional ZnCo/MoS2–Co3S4/NF heterostructure supported on nickel foam as highly efficient catalyst for hydrogen evolution reaction

Exploring inexpensive and earth-abundant electrocatalysts for hydrogen evolution reactions is crucial in electrochemical sustainable chemistry field. In this work, a high-efficiency and inexpensive non-noble metal catalysts as alternatives to hydrogen evolution reaction (HER) was designed by one-step hydrothermal and two-step electrodeposition method. The as-prepared catalyst is composed of the synergistic MoS₂–Co₃S₄ layer decorated by ZnCo layered double hydroxides (ZnCo-LDH), which forms a multi-layer heterostructure (ZnCo/MoS₂–Co₃S₄/NF). The synthesized ZnCo/MoS₂–Co₃S₄/NF exhibits a small overpotential of 31 mV and a low Tafel plot of 53.13 mV dec^?1 at a current density of 10 mA cm^?2, which is close to the HER performance of the overpotential (26 mV) of Pt/C/NF. The synthesized ZnCo/MoS₂–Co₃S₄/NF also has good stability in alkaline solution. The excellent electrochemical performance of ZnCo/MoS₂–Co₃S₄/NF electrode originates from its abundant active sites and good electronic conductivity brought by the multilayer heterostructure. This work provides a simple and feasible way to design alkaline HER electrocatalysts by growing heterostructures on macroscopic substrates.     

Co supported on Mg–La mixed oxides as an efficient catalyst for ammonia synthesis

Ammonia presents a promising hydrogen source and energy carrier for mobile and stationary applications. The development of new and cheaper catalysts for ammonia synthesis is thus of great importance in improving the efficiency of the Haber-Bosch process. Here we report the investigation of ammonia synthesis on cobalt catalysts supported on magnesium–lanthanum mixed oxides with varying Mg/La molar ratios. Our studies revealed that the catalyst's activity is tuneable by varying the support composition, allowing an adjustment of the surface adsorption properties. Owing to the increased basicity of the support and weaker interactions between cobalt and hydrogen atoms, the catalyst supported on mixed MgO–La₂O₃ oxide with Mg/La molar ratio of 7 demonstrated the highest activity and stability for ammonia synthesis as compared to other reported cobalt catalysts.     

Amorphous cobalt–boron/nickel foam as an effective catalyst for hydrogen generation from alkaline sodium borohydride solution

Low cost and catalytically effective transition metal catalysts are of interest for the development of on-board hydrogen generation systems for fuel-cell vehicles. In the present study a modified electroless plating method was developed for the preparation of amorphous Co–B catalyst supported on Ni foam. Compared to the conventional electroless plating method, the newly developed method is more effective and produces Co–B catalyst with much higher catalytic activity. The catalytic activity of the supported Co–B catalyst was found to be highly dependent on the plating times and calcination conditions. Through optimization of these preparation conditions we were able to prepare a catalyst capable of a hydrogen generation rate of 11 l (min g)⁻¹ (catalyst) in a 20 wt.% NaBH₄ + 10 wt.% NaOH solution. Preliminary phase analyses and microstructure characterization were performed to understand the effects of preparation conditions on the catalytic activity of the Co–B catalyst.     

Novel MoSe2–Ni(OH)2 nanocomposite as an electrocatalyst for high efficient hydrogen evolution reaction

Nowadays, there is a great demand for low-cost and highly active electrocatalyst for the production of clean renewable energy. However, most of the electrocatalysts are noble metal-based which are very costly and unstable. To counter this, electrochemical water splitting in energy storage systems is been widely applied, using non-noble metal-based nanostructured electrocatalysts. In this work, a novel noble metal-free MoSe₂–Ni(OH)₂ nanocomposite electrocatalyst is synthesized using a multi-step hydrothermal technique for efficient hydrogen evolution reaction (HER). The morphology, structural, chemical composition, and functional features of the synthesized nanomaterials were characterized using different techniques that include scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), and Raman analysis. The new developed MoSe₂–Ni(OH)₂ nanocomposite combines a high active surface area with a high chemical stability, generating a novel material with a synergistic effect that enhances water splitting process performance. Thus, an outstanding low Tafel slope of 54 mV dec⁻¹ is accomplished in the hydrogen evolution reaction.     

In-situ growth and electronic structure modulation of urchin-like Ni–Fe oxyhydroxide on nickel foam as robust bifunctional catalysts for overall water splitting

The rational design of non-precious-metal bifunctional catalysts of oxygen and hydrogen evolution reactions that generate a high current density and stability at low over potentials is of great significance in the field of water electrolysis. Herein, we report a facile and controllable method for the in-situ growth of urchin-like FeOOH–NiOOH catalyst on Ni foam (FeOOH–NiOOH/NF). X-ray photoelectron spectroscopy confirms that the proportion of Ni and Fe species with high valence state gradually increase with the extension of growth time. Electrochemical studies have shown that the optimized FeOOH–NiOOH/NF-24 h and −12 h catalysts demonstrate excellent electrochemical activity and stability in oxygen/hydrogen evolution reactions. Moreover, the cell voltage is reduced around 0.15 V at high current density (0.5–1.0 A cm⁻²) as compared to the state-of the art RuO₂/NF(+)||Pt–C/NF(−) system, far better than most of the previously reported catalysts. The cost analyst revealed that using FeOOH–NiOOH/NF catalyst as both electrodes could potentially reduce the price of H₂ around 7% compared with traditional industrial electrolyzers. These excellent electrocatalytic properties can be attributed to the unique urchin-like structure and the synergy between Ni and Fe species, which can not only provide more active sites and accelerate electron transfer, but also promote electrolyte transport and gas emission.     

Potentiostatic electrodeposited of Ni–Fe–Sn on Ni foam served as an excellent electrocatalyst for hydrogen evolution reaction

Ni–Fe–Sn electrocatalyst supported on nickel foam (Ni–Fe–Sn/NF) with high efficiency of hydrogen evolution reaction (HER) has been successfully fabricated through one-step potentiostatic electrodeposition route. The optimized Ni–Fe–Sn/NF displayed an extremely low overpotential of, respectively, 144 and 180 mV at 50 and 100 mA cm^?2 for HER in alkaline condition. Moreover, it could retain its superior stability for at least 12 h. The remarkable electrocatalytic activity of our electrocatalyst is ascribed to the high conductivity originated from synergistic effects between Ni, Fe, and Sn during HER process.     

Potentiostatic electrodeposition of cost-effective and efficient Ni–Fe electrocatalysts on Ni foam for the alkaline hydrogen evolution reaction

The hydrogen evolution reaction (HER) using earth-abundant noble-metal-free catalysts has gained substantial interest in electrocatalytic water splitting technologies, particularly in water-alkali electrolyzers. The development of highly-efficiency and durable inexpensive electrocatalysts to accelerate the kinetics of HER is still a formidable challenge. In this study, nickel–iron (Ni–Fe) electrocatalyst directly grown on backbones of Ni foam (NF) substrate was facile prepared via one-step potentiostatic electrodeposition method. The obtained Ni–Fe electrocatalyst exhibits a film-like structure. Owing to high electrical conductivity and composition optimization, the synthesized Ni–Fe electrocatalyst with Ni/Fe atomic ratio of c.a. 65:35 possesses an attractive electrocatalytic activity with low overpotentials of 142, 205, and 239 mV at 10, 50, and 100 mA·cm^?2 in alkaline electrolyte, respectively.     

One-step synthesis of oxygen incorporated V–MoS2 supported on partially sulfurized nickel foam as a highly active catalyst for hydrogen evolution

Highly active noble-metal-free catalysts for hydrogen evolution reaction (HER) are essential for the sustainable production of hydrogen. MoS₂ based HER catalysts are potentially competitive to noble metals but facing the challenges of low conductivity, density of active sites and intrinsic activity in basal planes. Herein, oxygen incorporated V–MoS₂ supported on partially sulfurized nickel foam (V–Mo(x)S/NF) are synthesized as binder-free HER catalysts via a one-step in-situ hydrothermal method. By controlling the fed atomic ratios of V/Mo, the optimal V–Mo(0.05)S/NF shows the low HER overpotential of ~31 and ~115 at 10 mA cm⁻² and 100 mA cm⁻², respectively in alkaline electrolyte, which is among the most active noble-metal and noble-metal-free HER catalysts reported. In V–Mo(0.05)S/NF, the introduced V and partially sulfurized nickel foam increases the conductivity. The hedgehog-like morphology ensures the exposure of high-density active sites. More importantly, the incorporated surface oxygen can be readily tuned by the fed atomic ratios of V/Mo, which plays the primary role in promoting the intrinsic HER activity for V–Mo(x)S/NF. This work demonstrates the feasibility of boosting HER through the precise control of incorporated surface oxygen in MoS₂ based catalysts.     

Co–NiFe layered double hydroxide nanosheets as an efficient electrocatalyst for the electrochemical evolution of oxygen

The development of non-precious metal catalysts for the electrochemical oxygen evolution reaction (OER) is especially important for the water electrolysis process. Herein, a two-dimensional (2D) ultrathin hybrid Co–NiFe layered double hydroxide (LDH) is synthesized via a facile hydrothermal method. In 1.0 M KOH electrolyte, Co–NiFe LDH exhibits remarkable activities for OER. At the current density of 10 mA cm⁻², it only needs an overpotential of 278 mV, which is ca. 50 mV and 20 mV lower than those for NiFe LDH (328 mV) and RuO₂ catalysts (298 mV), respectively. In addition, Co–NiFe LDH also shows impressive long-term stability for OER. Besides the stable morphology and crystal structure, the potential is always kept at 1.50 V and shows almost no attenuation during the 20 h of durability test. Changes in the electronic structure of LDH due to introduction of Co ions, as well as the large specific surface area facilitate the mass/electron transfer and the oxygen bubbles release, and thus lead to the enhanced catalytic properties for OER. This work can be informative not only for understanding the role of physical and electronic structures on OER but also for designing high-performance non-precious metal OER electrocatalysts.     

Vertical Nickel–Iron layered double hydroxide nanosheets grown on hills-like nickel framework for efficient water oxidation and splitting

Herein, the vertical thin nickel–iron layered double hydroxide nanosheets grown on the hills-like nickel framework (NiFe LDH/Ni@NF) are employed for the oxygen evolution reaction (OER), securing at the low overpotentials of 197 and 270 mV to obtain the current densities of 20 and 100 mA cm⁻², respectively, with a Tafel slope of 73.34 mV dec⁻¹. The electrodeposited nickel film induces the NiFe LDH nanosheets grow vertically and thinly. As well, the nickel abundant interfaces and inner space makes this catalyst effective for OER. It was further served as the OER electrode in a water splitting system coupled the Pt/C cathode, and a cell voltage was at 1.52 and 1.67 V to achieve the current density of 10 mA cm⁻² and 50 mA cm⁻². In addition, the water electrolyzer can suffer a long time of 24 h at 50 mA cm⁻², showing the feasibility in a practical unbiased alkaline water splitting system.     

Graphene–sulfur–Ni(OH)2 sandwich foam composites as free-standing cathodes for high-performance Li–S batteries

Lithium–sulfur (Li–S) batteries are considered as a next-generation energy storage solution thanks to the dramatic increase in their energy density and the accompanying low fabrication cost. Nonetheless, their practical applications have been hampered by critical challenges such as cycling instability, low sulfur utilisation and efficiency. Here, the interfacial growth of Ni(OH)₂-encapsulated sulfur nanoparticles in a reduced graphene oxide free-standing matrix as Li–S cathodes has been highlighted, along with a detailed application investigation of the sandwich foam structure in Li–S batteries. Compared to sulfur composites based solely on a graphene host (S@rGO), this composite foam cathode could provide significant improvements in specific capacity and long-cycle stability with the effective confinement and promoted conversion of lithium polysulfides. Moreover, the sandwich foam composite cathode exhibits a high specific capacity of 1189 mA h g⁻¹ (0.1 C), better rating performance (691 mA h g⁻¹ at 2 C) and remarkable cycling stability, retaining 81% of the initial capacity after 200 cycles of charge–discharge at 0.2 C. Furthermore, Ni(OH)₂ wrapping at the cathode–electrolyte interface offers vastly improved polysulfide shuttle suppression, which provides a new cathode encapsulation method for further developments of advanced Li–S cathodes.     

Pulse-electrodeposited Ni–Fe–Sn films supported on Ni foam as an excellent bifunctional electrocatalyst for overall water splitting

The development of extremely active bifunctional non-noble electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is pivotal for water splitting but remains challenging. Herein, self-supported Ni–Fe–Sn electrocatalysts were fabricated on nickel foam (NF) through a simple and facile pulse electrodeposition process. Under optimal conditions, the prepared Ni–Fe–Sn electrocatalysts exhibited excellent bifunctional properties in alkaline medium and required ultralow overpotentials of only 27 and 201 mV for HER and OER, respectively, to reach the current density of 10 mA cm^?2. Importantly, the same Ni–Fe–Sn electrocatalyst can be assembled as the anode and the cathode in a two-electrode system. It demanded a fairly low applied voltage of 1.55, 1.72, and 1.87 V to produce 10, 50, and 100 mA cm^?2, respectively, and exhibited excellent long-term stability. The excellent electrocatalytic water splitting performance of the Ni–Fe–Sn film was mainly associated with its intrinsic catalytic activity derived from the modulation of the electronic structures among Ni, Fe, and Sn by using the appropriate atomic ratio of Ni: Fe: Sn.     

Controlled synthesis of Mn3O4/Co9S8–Ni3S2 on nickel foam as efficient electrocatalyst for oxygen evolution reaction

Advances in electrochemical interfaces have greatly facilitated the development of new energy systems that can replace traditional fossil fuels. Oxygen evolution reaction (OER) is the core reaction in the new energy conversion system to produce hydrogen. Here, nanorods structure of Mn₃O₄/Co₉S₈–Ni₃S₂/NF-4 was designed and assembled. The Mn₃O₄ has served as an appropriate matrix to build a composite structure with Co₉S₈–Ni₃S₂ to enhance the stability of catalyst. And the introduction of Mn regulated the electronic structure of Ni and Co, which increased the OER activity of matericals. Further characterization and electrochemical testing have suggested that between polymetallic can effectively optimize conductivity and enhance reaction kinetics. Mn₃O₄/Co₉S₈–Ni₃S₂/NF-4 can achieve overpotential of 188 mV at the current density of 10 mA cm^?2 in alkaline solution, with small Tafel slope of 43.2 mV dec^?1 and satisfactory stability of 30 h at 10 mA cm^?2. This work may show a feasible reference in the design of high-efficient OER catalysts.     

Pd,Pd–Ni and Pd–Ni–Fe nanoparticles anchored on MnO2/Vulcan as efficient ethanol electro-oxidation anode catalysts

Pd–Ni–Fe nanoparticles supported on MnO₂/Vulcan XC-72 R (carbon black powder) as the electrocatalyst for the anodic oxidation of ethanol in a direct ethanol alkaline fuel cell (DEAFC) has been conducted. Electrocatalyst structures and morphologies are investigated by XRD, FE-SEM, EDX and elemental mapping techniques and subsequently electrochemical performance of electrocatalysts for ethanol oxidation reaction (EOR) are studied by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). Pd/MnO₂/Vulcan, Pd–Ni/MnO₂/Vulcan and Pd–Ni–Fe/MnO₂/Vulcan efficiently advanced ethanol electro-oxidation reaction under alkaline conditions. Pd/MnO₂/Vulcan revealed best potential window and low charge transfer resistance (R_ct) for EOR. Pd–Ni/MnO₂/Vulcan and Pd–Ni–Fe/MnO₂/Vulcan electrocatalysts have a good anti CO-poisoning capability. Pd–Ni–Fe/MnO₂/Vulcan has significantly high current density, excellent catalyst durability and cyclic stability for ethanol oxidation which encourage researchers for application of such exceptional materials as anode electrocatalysts in DEFC.     

Direct synthesis of binder-free Ni–Fe–S on Ni foam as superior electrocatalysts for hydrogen evolution reaction

Designing the efficient, low-cost and stable electrocatalyst is of great significance for storage and conversion of the renewable energy to hydrogen. Herein, the binder-free Ni–Fe–S electrocatalysts were directly electrodeposited on Ni foam, which exhibited the excellent hydrogen evolution reaction performance with the overpotential of 51.4 mV at the current density of 10 mA cm^?2. Based on the analysis and results of as-synthesized Ni, Ni–Fe and Ni–S, the boosted electrocatalytic activity can be attributed to the composite effect between Ni and the introduced Fe and S. Additionally, the Ni–Fe–S electrocatalysts also displayed the low cell voltage (1.59 V at 10 mA cm^?2), remarkable durability and high Faraday efficiency in overall water electrocatalysis. Moreover, the water electrolysis device with Ni–Fe–S bi-electrodes can be driven by a small wind power generation and producing 4 mL H₂ in 39 min, indicating the prepared Ni–Fe–S electrocatalyst has the great potentials in producing hydrogen via renewable energy.     

Synthesis of an active and stable Ptshell–Pdcore/C catalyst for the electro-oxidation of methanol

A Pt_shell–Pd_core/C catalyst is prepared via electroless deposition and galvanic displacement. The catalyst is active toward the electro-oxidation of methanol and is more stable against CO_ad-poisoning than a commercial Pt/C catalyst. The stable activity of Pt_shell–Pd_core/C is ascribed to the tuned electronic property of the Pt over-layer in the Pt_shell–Pd_core/C, which leads to weak binding with CO_ad and increases the kinetics of OH_ad formation. The weakened binding property of the surface Pt with CO_ad and the facile oxidation of CO_ad by OH_ad were confirmed by a spectroscopic analysis and in a CO_ad-stripping experiment, respectively. The electro-oxidation of CO_ad by OH_ad is the rate-determining step of methanol oxidation. Therefore, the accelerated formation of OH_ad contributes to the overall oxidation reaction, preventing CO_ad-poisoning. In addition, Pt_shell–Pd_core/C maintains its activity longer than Pt/C does during a prolonged cycle experiment.     

Synthesis and optimization of Mo–Ni–Se@NiSe core-shell nanostructures as efficient and durable electrocatalyst for hydrogen evolution reaction in alkaline media

Synthesis conditions are among the most influential factors in the electrocatalytic properties of the samples studied for the hydrogen evolution reaction (HER). In this study, conditions of NiSe synthesis over a Mo–Ni–Se layer were optimized to create core-shell nanostructures with excellent electrocatalytic properties. To optimize the synthesis conditions, first, two electrodeposition techniques in constant potential and pulse potential conditions were investigated and then the optimal temperature for electrodeposition between 5, 25, 40, and 60 °C was found. The electrocatalytic activity of the synthesized samples was investigated using linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry tests in a 1 M KOH solution. Preliminary results showed that pulsed electrodeposition of NiSe could improve the electrocatalytic activity of Mo–Ni–Se by forming durable and suitable nanostructures, while electrodeposited NiSe at constant potential could reduce the electrocatalytic activity of the electrode by forming a dense structure. Then, to determine the appropriate temperature, electrodeposition at the optimal pulse potential at four temperatures of 5, 25, 40, and 60 °C was used to synthesize NiSe on Mo–Ni–Se. The final results showed that the sample synthesized at 60 °C with an electrochemically active surface area of 2870 cm² had the highest hydrogen production sites and required only an overpotential of 77 mV to achieve a current density of 10 mA cm^?2.