Nanocrystalline cobalt–nickel–boron (metal boride) catalysts for efficient hydrogen production from the hydrolysis of sodium borohydride

Innovative metal boride nanocatalysts containing crystalline Co–Ni based binary/ternary boride phases were synthesized and used in the hydrolysis of NaBH₄. All the as-prepared catalysts were in high-purity with average particle sizes ranging between ~51 and 94 nm and consisting of different crystalline phases (e.g. CoB, Co₂B, Co₅B₁₆, NiB, Ni₄B₃, Ni₂Co_0·67B_0.33). The synergetic effect of the different binary/ternary boride phases in the composite catalysts had a positive role on the catalytic performances thus, while the binary boride containing phases of unstable cobalt borides or single Ni₄B₃ were not showing any catalytic activity. The Co–Ni–B based catalyst containing crystalline phases of CoB–Ni₄B₃ exhibited the highest H₂ production rate (500.0 mL H₂ min^?1 g_cat^?1), with an apparent activation energy of 32.7 kJ/mol. The recyclability evaluations showed that the catalyst provides stability even after the 5th cycle. The results suggested that the composite structures demonstrate favorable catalytic properties compared to those of their single components and they can be used as alternative and stable catalysts for efficient hydrogen production from sodium borohydride.     

Cobalt nickel boride nanocomposite as high-performance anode catalyst for direct borohydride fuel cell

Similar to MXene, MAB is a group of 2D ceramic/metallic boride materials which exhibits unique properties for various applications. However, these 2D sheets tend to stack and therefore lose their active surface area and functions. Herein, an amorphous cobalt nickel boride (Co–Ni–B) nanocomposite is prepared with a combination of 2D sheets and nanoparticles in the center to avoid agglomeration. This unique structure holds the 2D nano-sheets with massive surface area which contains numerous catalytic active sites. This nanocomposite is prepared as an electrocatalyst for borohydride electrooxidation reaction (BOR). It shows outstanding catalytic activity through improving the kinetic parameters of BH₄^? oxidation, owing to abundant ultrathin 2D structure on the surface, which provide free interspace and electroactive sites for charge/mass transport. The anode catalyst led to a 209 mW/cm² maximum power density with high open circuit potential of 1.06 V at room temperature in a miniature direct borohydride fuel cell (DBFC). It also showed a great longevity of up to 45 h at an output power density of 64 mW/cm², which is higher than the Co–B, Ni–B and PtRu/C. The cost reduction and prospective scale-up production of the Co–Ni–B catalyst are also addressed.     

Efficient overall water splitting using nickel boride-based electrocatalysts

Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (Fe_xNi_1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe_0.2Ni_0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe_0.2Ni_0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm⁻² at a voltage of only 1.62 V. Further, the Fe_0.2Ni_0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.     

Facile one-pot synthesis of binder-free nano/micro structured dendritic cobalt activated nickel sulfide: a highly efficient electrocatalyst for oxygen evolution reaction

Reasonable design and preparation of non-noble metal electrocatalysts with predominant catalytic activity and long-term stability for oxygen evolution reaction (OER) are essential for electrocatalytic water splitting. Ni foam (NF) is highlighted for its 3D porous structure, impressive conductivity and large specific surface area. Herein, nano/micro structured dendritic cobalt activated nickel sulfide grown on 3D porous NF (Co–Ni₃S₂/NF) has been successfully synthesized by one-step hydrothermal method. Due to the ingenious incorporation of Co, Co–Ni₃S₂/NF electrode shows auspicious electrocatalytic performance for OER compared with Ni₃S₂/NF electrode. As a result, Co–Ni₃S₂/NF needs overpotential of only 274 and 459 mV at current density of 10 and 50 mA cm⁻², respectively, while Ni₃S₂/NF requires overpotential of 344 and 511 mV. At potential of 2.0 V (vs. RHE), Co–Ni₃S₂/NF displays current density of 191 mA cm⁻², while Ni₃S₂/NF just attains current density of only 135 mA cm⁻². Moreover, Co–Ni₃S₂/NF demonstrates excellent stability for uninterrupted OER in alkaline electrolyte. The strategy of designing and preparing cobalt activated nickel sulfide grown on NF renders a magnificent prospect for the development of metal-sulfide-based oxygen evolution catalysts with excellent electrocatalytic performances.     

A high-performance oxygen evolution electrocatalyst based on partially amorphous bimetallic cobalt iron boride nanosheet

The oxygen evolution reaction (OER) plays a crucial role in various electrochemical energy conversion devices, but it greatly suffers from sluggish kinetic. Therefore, developing economical and high-active electrocatalysts with superior durability and high efficiency for OER is still a huge challenge. Herein, a partially amorphous nanosheet-liked bimetallic cobalt iron boride is directly grown on the nickel foam (CoFeB-5-30 NS/NF) via a facile electroless plating method and adopted as a catalyst for OER. Benefiting from the rational designed nanosheet array which provides large surface areas and more open-pathways to obtain fast electron transportation and gas release, the resulted CoFeB-5-30 NS/NF catalyst exhibits excellent catalytic activity and superior electrochemical stability in alkaline medium. The obtained CoFeB-5-30 NS/NF exhibits an overpotential of 260 mV to reach the current density of 20 mA cm⁻². Most importantly, the CoFeB-5-30 NS/NF possesses a small Tafel slope of 38 mV dec⁻¹ and excellent stability with insignificant activity degradation after successive electrolytic measurement (for over 60 h) at 20, 50 and 100 mA cm⁻² in 1.0 M KOH, respectively. This work provides a simple and rapid strategy to prepare bimetallic borides and broadens the way for the development of efficient OER catalysts.     

Nickel nanorods over nickel foam as standalone anode for direct alkaline methanol and ethanol fuel cell

A highly electroactive nickel nanorod (NNR)/nickel foam (NF) electrode was fabricated for direct alcohol fuel cells (DAFCs) using a simple and cost-effective hydrothermal process. The Ni/NiO nanorods were successfully grown on the surface of an NF electrode, which strongly enhanced the anode wettability and increased surface area by 18 times (11.9 m² g⁻¹), resulting in interfacial polarization resistance reduction. The NNR/NF electrode shows high electro-catalytic activity and great stability during alcohol oxidation. The current densities obtained for NNR/NF were four (479 mA cm⁻²) and six (543 mA cm⁻²) times higher than that for pristine NF in the cases of methanol and ethanol oxidations, respectively. This high current density can be attributed to the superhydrophilic surface of the Ni/NiO nanorods and corresponding high mass transfer capability between the electrolytes and Ni/NiO nanorods embedded on the surface of the electrodes. This study presents a new approach for using the novel NNR/NF as a cheap and high performance anode in DAFCs.     

Multifunctional Co–B–O@CoxB catalysts for efficient hydrogen generation

The development of efficient and non-noble catalyst is of great significance to hydrogen generation techniques. Three surface-oxidized cobalt borides of Co–B–O@Co_xB (x = 0.5, 1 and 2) have been synthesized that can functionalize as active catalysts in both alkaline water electrolysis and the hydrolysis of sodium borohydride (NaBH₄) solution. It is discovered that oxidation layer and low boron content favor the oxygen evolution reaction (OER) activity of Co–B–O@Co_xB in alkaline water electrolysis. And surface-oxidized cobalt boride with low boron content is more active toward hydrolysis of NaBH₄ solution. An alkaline electrolyzer fabricated using the optimized electrodes of Co–B–O@CoB₂/Ni as cathode and Co–B–O@Co₂B/Ni as anode can deliver current density of 10 mA cm⁻² at 1.54 V for overall water splitting with satisfactory stability. Meanwhile, Co–B–O@Co₂B affords the highest hydrogen generation rate of 3.85 L min⁻¹ g⁻¹ for hydrolysis of NaBH₄ at 25 °C.     

Engineering hierarchical NiFe-layered double hydroxides derived phosphosulfide for high-efficiency hydrogen evolving electrocatalysis

Exploring robust, highly efficient, and cost-effective non-noble metal electrocatalysts for replacing Pt in hydrogen evolution reaction (HER) is of great significance. In this study, we skillfully synthesized binary transition-metal (i.e., nickel and iron) phosphosulfides on nickel foam (NiFeSP/NF) via a sulfuration/phosphorization treatment of bimetallic layered double hydroxides (LDH). Taking the advantage of the presence of active heterointerfaces among Ni₂P, Ni₃S₂, and FeS₂, the NiFeSP/NF catalyst, which was advantageous of the highly exposed active sites, exhibited an extraordinary catalytic activity in HER—an overpotential of 70 mV at a current density of 10 mA cm⁻² and a Tafel slope of 69 mV dec⁻¹, outperforming most of the existing counterparts. Moreover, NiFeSP/NF catalysts demonstrated favorable long-term catalytic stability for 10 h. We contributed this superior catalytic activity to the characteristic attributes of NiFeSP/NF, which could be stemmed from its exquisite catalyst design: (i) the co-occurrence of highly HER-favored crystalline Ni₂P, Ni₃S₂, and FeS₂ in bimetallic phosphosulfides and (ii) the existence of multi-functional phase interfaces among Ni₂P, Ni₃S₂, and FeS₂ in the NiFeSP/NF hierarchical structure. The present study exemplified an effective strategy for designing HER-favored bimetallic phosphosulfides and provided the scientific base for the insight into the catalytic nature of multi-metallic phosphosulfides.     

Porous flower-like nickel nitride as highly efficient bifunctional electrocatalysts for less energy-intensive hydrogen evolution and urea oxidation

Finding a suitable replacement for the high potential of anodic water electrolysis (oxygen evolution reaction (OER)) is significant for hydrogen energy storage and conversion. In this work, a simple and scalable method synthesizes a structurally unique Ni₃N nanoarray on Ni foam, Ni₃N-350/NF, that provides efficient electrocatalysis for the urea oxidation reaction (UOR) that transports 10 mA cm⁻² at a low potential of 1.34 V. In addition, Ni₃N-350/NF exhibits electro-defense electrocatalytic performance for hydrogen evolution reaction, which provides a low overpotential of 128 mV at 10 mA cm⁻². As proof of concept, all-water-urea electrolysis measurement is carried out in 1 M KOH with 0.5 M Urea with Ni₃N-350/NF as cathode and anode respectively. Ni₃N-350/NF||Ni₃N-350/NF electrode can provide 100 mA cm⁻² at a voltage of only 1.51 V, 160 mV less than that of water electrolysis, which proves its commercial viability in energy-saving hydrogen production.     

Engineering bimetallic cactus-like NiFeOOH/CoNiSe2 heterostructure nanosheets for efficient oxygen evolution and overall water splitting

The development of structural stable, high-performance, inexpensive electrocatalysts for oxygen evolution reactions (OER) is essential to alleviate the energy crisis. Herein, cactus-like CoNiSe₂ was synthesized on nickel foam and NiFeOOH was electrodeposited on surface of CoNiSe₂ to form a core-shell structural electrode. The obtained NiFeOOH/CoNiSe₂/NF exhibited ultra-low overpotentials of 204 mV and 234 mV at 10 and 100 mA cm⁻², with a Tafel slope of 26.2 mV dec⁻¹ in 1 M KOH alkaline solution. Furthermore, the current density only decreased by 5% after a 100 h durability test at 200 mA cm⁻², showing excellent robust stability. A two-electrode system with NiFeOOH/CoNiSe₂/NF as anode and Ni/NiO@MoO_3-x/NF as cathode (NiFeOOH/CoNiSe₂/NF||Ni/NiO@MoO_3-x/NF) showed a low voltage of 1.47/1.56 V to deliver 10/100 mA cm⁻². According to the experimental and density functional theory (DFT) results, the strong electronic interactions at the NiFeOOH/CoNiSe₂/NF interface leads to an increase in the valence state of Fe and an optimisation of the adsorption free energy, which are favourable to reduce the energy consumption of the OER. This work obtained high performance OER electrocatalysts by engineering amorphous and crystalline heterointerfaces and structural design, which will provide some inspiration for similar work.     

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.     

Porous Ni2P nanoflower supported on nickel foam as an efficient three-dimensional electrode for urea electro-oxidation in alkaline medium

Porous Ni₂P nanoflower supported on nickel foam (Ni₂P@Ni foam) electrodes are synthesized via a simple hydrothermal growth strategy accompanied with further phosphating treatment. The prepared electrodes are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). Electro-catalytic performances towards urea electro-oxidation are tested by cyclic voltammetry (CV), chronoamperometry (CA) coupled with electrochemical impedance spectroscopy (EIS). By phosphating Ni(OH)₂ precursor, the final obtained Ni₂P@Ni foam electrode presents a porous Ni₂P nanoflower structure within abundant porosity, and so exposes a large amount of electro-catalytic active sites and electronic transmission channels to accelerate the interfacial reaction. Compared with Ni(OH)₂@Ni foam precursor, the Ni₂P@Ni foam catalyst exhibits more excellent electro-catalytic activity as well as lower onset oxidation potential. Remarkably, the Ni₂P@Ni foam catalyst reaches a peak current density of 750 mA cm^?2 with an onset oxidation potential of 0.24 V (vs. Ag/AgCl) accompanied by an excellent stability in 0.60 M urea with 5.00 M KOH solutions. Benefiting from the unique porous nanosheet structure, the as-synthesized Ni₂P@Ni foam catalyst performs a highly enhanced catalytic behavior for alkaline urea electro-oxidation, indicating that the material can be hopefully applied in direct urea fuel cells.     

In situ growth Fe and V co-doped Ni3S2 for efficient oxygen evolution reaction at large current densities

Industrial electrolysis of water is one of the effective strategies for green hydrogen production in the future. Nevertheless, the large-scale applications of water electrolysis are still intractable issues hindered by the high overpotentials and inferior reaction kinetics on the anode. Herein, a facile one-step hydrothermal method was applied to in situ growth the Fe and V co-doped Ni₃S₂ electrocatalyst on nickel foam substrate (Fe, V–Ni₃S₂/NF). In 1 M KOH electrolyte, the as-prepared Fe, V–Ni₃S₂/NF electrode exhibited an improved water oxidation activity with ultralow overpotentials of 253 and 370 mV to realize large current densities of 100 and 1000 mA/cm², respectively. More importantly, the Fe, V–Ni₃S₂/NF electrode existed an activation process during 100 h chronopotentiometry testing period. Detailed characterizations revealed that elements of V and S in the electrocatalyst were oxidized and dissolved into the electrolyte, making the electrocatalyst undergo surface reconstruction and resulting in a faster kinetic reaction rate, thus leading to enhanced oxygen evolution reaction activities. Collectively, the resultant Fe, V–Ni₃S₂/NF in this work provides new cogitation towards design and synthesis of low-cost electrocatalyst with large current densities for water oxidation.     

Hydrogen evolution reaction in full pH range on nickel doped tungsten carbide nanocubes as efficient and durable non-precious metal electrocatalysts

Design of novel inexpensive non-precious metal electrocatalysts to replace Pt based electrocatalysts for wide pH range hydrogen evolution reaction (HER) still remains great challenges and opportunities, for globally sustainable supply of clean hydrogen. Ni doped tungsten carbide nanocubes supported on Ni foam (W_1-xNi_xC NCs/NF) synthesized via a hydrothermal-carbonization methods is reported. W_1-xNi_xC NCs/NF electrocatalysts exhibit excellent catalytic performance with overpotentials lower than 50 mV in both acidic, alkaline and neutral medium. Meanwhile, large electrochemical surface area and better conductivities of W_1-xNi_xC NCs/NF electrocatalysts are deemed in favour of its efficient catalytic properties. Moreover, the electrocatalysts show superior stability in wide pH range. It is believed that the present work provides a novel strategy for designing low-cost and efficient pH universal non-precious metal electrocatalysts for HER.     

Enhanced oxygen evolution reaction activity of NiFe layered double hydroxide on nickel foam- reduced graphene oxide interfaces

Herein, we prepared a novel nickel iron-layered double hydroxide/reduced graphene oxide/nickel foam (NiFe-LDH/RGO/NF) electrodes by two step electrodeposition processes for oxygen evolution reaction (OER). The modification of NF by RGO increased the interface conductivity and electrochemical active surface areas (ECSA) of the electrode. The NiFe-LDH/RGO/NF electrode has shown higher catalytic activity with a lower overpotential of 150 mV at the current density of 10 mA cm⁻². The NiFe-LDH/RGO/NF electrode has also shown a small Tafel slope of 35 mV per decade due to the synergy effect between the larger ECSA and the conductive RGO interface. Furthermore, the electrodes exhibits almost 10 h stability under a general current density of 10 mA cm⁻².     

Carbon-ceramic supported bimetallic Pt–Ni nanoparticles as an electrocatalyst for electrooxidation of methanol and ethanol in acidic media

The electrooxidation of methanol and ethanol was investigated in acidic media on the platinum–nickel nanoparticles carbon-ceramic modified electrode (Pt–Ni/CCE) via cyclic voltammetric analysis in the mixed 0.5 M methanol (or 0.15 M ethanol) and 0.1 M H₂SO₄ solutions. The Pt–Ni/CCE catalyst, which has excellent electrocatalytic activity for methanol and ethanol oxidation than the Pt–Ni particles glassy carbon modified electrode (Pt–Ni/GCE), Pt nanoparticles carbon-ceramic modified electrode (Pt/CCE) and smooth Pt electrode, shows great potential as less expensive electrocatalyst for these fuels oxidation. These results showed that the presence of Ni in the structure of catalyst and application of CCE as a substrate greatly enhance the electrocatalytic activity of Pt towards the oxidation of methanol and ethanol. Moreover, the presence of Ni contributes to reduce the amount of Pt in the anodic material of direct methanol or ethanol fuel cells, which remains one of the challenges to make the technology of direct alcohol fuel cells possible. On the other hand, the Pt–Ni/CCE catalyst has satisfactory stability and reproducibility for electrooxidation of methanol and ethanol when stored in ambient conditions or continues cycling making it more attractive for fuel cell applications.     

Coupling NixSy-Ni2P heterostructure nanoarrays on Ni foam as environmentally friendly electrocatalyst for overall water splitting

The development of efficient, cheap and stable electrodes is the key to achieve the industrialization of hydrogen production from electrochemical water splitting. In this paper, Ni_xS_y-Ni₂P mixtures on Ni foam (Ni_xS_y-Ni₂P/NF) were synthesized by hydrothermal process followed by sulfurization and phosphorization approach. The combination of Ni_xS_y and Ni₂P exposes a large number of active sites, thus greatly improving the catalytic activity of the material. As expected, the Ni_xS_y-Ni₂P/NF material exhibits ultra-small overpotentials of 211 and 320 mV for water oxidation reaction at the current densities of 10 and 100 mA/cm², respectively. What is noteworthy is that the material also present superior hydrogen evolution reaction properties (122 mV@10 mA cm^?2). Moreover, when the material is acted as a bifunction electrode to drive the overall water splitting, only a cell voltage of 1.54 V is required to drive a current density of 10 mA/cm², which is one of the superior catalytic properties reported up to now. Experimental results show that the good electrochemistry performance of the Ni_xS_y-Ni₂P/NF material is attributed to the improved charge transfer rate, exposure of more active site and superior electrical conductivity. This work provides an effective way to explore environmentally friendly catalysts based on transition metal sulfide and phosphide.     

Self-supported cobalt–molybdenum oxide nanosheet clusters as efficient electrocatalysts for hydrogen evolution reaction

In this paper, we report the three-dimensional self-supported CoMoO₄ nanosheet clusters on the nickel foam (denoted as CoMoO₄/NF) by a facile hydrothermal-calcination method for efficient hydrogen generation. As a result, the freestanding CoMoO₄ electrode exhibits an efficient electrochemical activity towards hydrogen evolution reaction, showing overpotentials as low as 68 and 178 mV at current densities of 10 and 100 mA cm⁻² in the alkaline condition (1 M KOH), respectively, a Tafel slope value of 82 mV per decade. Moreover, the electrode exhibits remarkable electrochemical durability for 1000 cycles. Significantly, the water splitting electrolyzer assembled with CoMoO₄/NF || NiFe LDH/NF (the nickel iron layered double hydroxide supported on the nickel foam) system achieved 20 mA cm⁻² at 1.63 V, showing the CoMoO₄/NF is promising for practical water splitting applications.     

Hierarchical flower-like amorphous nickel sulfide/crystalline CoFe layered double hydroxide heterostructure for overall water splitting

The construction of a bifunctional electrocatalyst with excellent performance and low cost plays a key role in the application prospect of renewable energy. Herein, nickel sulfide/CoFe layered double hydroxide heterostructures on nickel foam (NiS/LDH/NF) have been constructed by using hydrothermal and electro-deposition methods. The amorphous nickel sulfide is deposited on the surface of crystalline LDH mesh-like nanosheets to form a hierarchical flower-like structure. The deposition of amorphous NiS can control the morphology and modulate the electronic structure of NiS/LDH/NF. The obtained NiS/LDH/NF is employed as a bifunctional catalyst for overall water splitting, which can achieve a current density of 10 mA cm^?2 at a low voltage of 1.51 V in 1 M KOH. The results show that the high electrocatalytic activity is ascribed to the formation of amorphous NiS/crystalline LDH heterostructure with abundant surface defects and active sites. The synthetic strategy holds a great promise for accelerating the development of hydrogen energy by highly efficient electrocatalytic production of hydrogen.     

Self-supported Ni3N nanoarray as an efficient nonnoble-metal catalyst for alkaline hydrogen evolution reaction

Efficient, robust and low-cost hydrogen evolution reaction (HER) electrodes are highly desirable for realizing the hydrogen economy. Transition metal nitrides with suitable hydrogen adsorption energy have been demonstrated as excellent HER catalysts. Here, we report a simple one-step nitridation method to fabricate Ni₃N nanorod arrays on nickel foam (NF) for electrocatalytic water splitting. Large specific surface area and good conductivity endow the self-supported Ni₃N/NF electrode extremely low overpotential of η₁₀ = 45 mV and excellent cycle stability for the HER in 1 M KOH aqueous solution. Based on theoretical calculations, it is further verified that nitridation effectively endows NF more suitable free energy for hydrogen adsorption, which leads to an advanced HER activity of Ni₃N/NF.