Electrodeposited Ni-Co-Sn alloy as a highly efficient electrocatalyst for water splitting

Water splitting to produce hydrogen and oxygen is considered as a feasible solution to solve the current energy crisis. It is highly desirable to develop inexpensive and efficient electrocatalyst for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this paper, nanostructured Ni-Co-Sn alloys were electrodeposited on copper foil and the excellent electrocatalytic performances for both HER and OER in alkaline media were achieved. The optimized Ni-Co-Sn electrode shows a low onset overpotential of −18 mV and a small Tafel slope of 63 mV/dec for the HER, comparable to many state-of-the-art non-precious metal HER catalysts. For the OER, it produces an overpotential of 270 mV (1.50 V vs. RHE) at current density of 10 mA/cm², which is better than that of the commercial Ir/C catalyst. In addition to high electrocatalytic activities, it exhibits good stability for both HER and OER. This is the first report that Ni-Co-Sn is served as a cost-effective and highly efficient bifunctional catalyst for water splitting and it will be of great practical value.     

Highly efficient and stable bifunctional electrocatalyst for water splitting on Fe–Co3O4/carbon nanotubes

Replacement of precious platinum (Pt) or ruthenium oxide (RuO₂) catalysts with efficient, cheap and durable electrocatalysts from earth-abundant elements bifunctional alternatives would be significantly beneficial for key renewable energy technologies including overall water splitting and hydrogen fuel cells. Despite tremendous efforts, developing bifunctional catalysts with high activity at low cost still remain a great challenge. Here, we report a nanomaterial consisting of core-shell-shaped Fe–Co₃O₄ grown on carbon nanotubes (Fe–Co₃O₄/CNTs) and employed as a bifunctional catalyst for the simultaneous electrocatalysts on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Fe–Co₃O₄/CNTs electrocatalyst outperforms the commercial RuO₂ catalyst in activity and stability for OER and approaches the performance of Pt/C for HER. Particularly, it shows superior electrocatalytic activity with lowering overpotentials of 120 mV at 10 mA cm^?2 for HER and of 300 mV at 10 mA cm^?2 for OER in 1 M KOH solution. The superior catalytic activity arises from unique core-shell structure of Fe–Co₃O₄ and the synergetic chemical coupling effects between Fe–Co₃O₄ and CNTs.     

Tungsten promoted nickel phosphide nanosheets supported on carbon cloth: An efficient and stable bifunctional electrocatalyst for overall water splitting

It is of great significance to develop a highly active, durable and inexpensive bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a tungsten-doped nickel phosphide nanosheets based on carbon cloth (W–Ni₂P NS/CC) as an efficient bifunctional catalyst through simple hydrothermal and phosphorization for overall water splitting in 1 M KOH. The W–Ni₂P NS/CC exhibits excellent electrochemical performance with low overpotentials for HER (η₁₀ = 71 mV, η₅₀ = 160 mV) and OER (η₂₀ = 307 mV, η₅₀ = 382 mV) in 1 M KOH, as well as superior long-term stability. Moreover, W–Ni₂P NS/CC as a bifunctional catalyst reveals remarkable activity with a low voltage of 1.55 V to reach a current density of 20 mA cm⁻². This work provides a viable bifunctional catalyst for the overall water splitting.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

MoS2/NiFeS2 heterostructure as a highly efficient electrocatalyst for overall water splitting at high current densities

Searching for efficient, stable and low-cost nonprecious catalysts for oxygen and hydrogen evolution reactions (OER and HER) is highly desired in overall water splitting (OWS). Herein, presented is a nickel foam (NF)-supported MoS₂/NiFeS₂ heterostructure, as an efficient electrocatalyst for OER, HER and OWS. The MoS₂/NiFeS₂/NF catalyst achieves a 500 mA cm⁻² current density at a small overpotential of 303 mV for OER, and 228 mV for HER. Assembled as an electrolyzer for OWS, such a MoS₂/NiFeS₂/NF heterostructure catalyst shows a quite low cell voltage (≈1.79 V) at 500 mA cm⁻², which is among the best values of current non-noble metal electrocatalysts. Even at the extremely large current density of 1000 mA cm⁻², the MoS₂/NiFeS₂/NF catalyst presents low overpotentials of 314 and 253 mV for OER and HER, respectively. Furthermore, MoS₂/NiFeS₂/NF shows a ceaseless durability over 25 h with almost no change in the cell voltage. The superior catalytic activity and stability at large current densities (>500 mA cm⁻²) far exceed the benchmark RuO₂ and Pt/C catalysts. This work sheds a new light on the development of highly active and stable nonprecious electrocatalysts for industrial water electrolysis.     

Combustion-derived BaNiO3 nanoparticles as a potential bifunctional electrocatalyst for overall water splitting

Electrochemical water electrolyser though an assuring solution for clean hydrogen production, the sluggish kinetics and high cost of existing precious metal electrocatalyst remains a barrier to its effective utilization. Herein, solution combustion route derived perovskite type barium nickelate (BaNiO₃) nanoparticles were developed and studied for their bifunctional electrocatalytic properties towards overall water splitting. The unannealed BaNiO₃ nanoparticles exhibited the highest OER and HER activity with overpotentials 253 mV and 427 mV respectively to attain 10 mAcm⁻² in 1.0 M KOH. Using unannealed BaNiO₃ as a bifunctional electrocatalyst in a two-electrode alkaline electrolyser, the cell was able to achieve the benchmark current density at a low cell voltage of 1.82 V. Impressively the setup's electrocatalytic performance improved 4.9% after continuous overall water splitting for 24 h at 30 mAcm⁻². Therefore, BaNiO₃ nanoparticles can be a low-cost and efficient alternative for noble metal electrocatalysts for clean H₂ production.     

Boosting the kinetics of oxygen and hydrogen evolution in alkaline water splitting using nickel ferrite /N-graphene nanocomposite as a bifunctional electrocatalyst

Design, synthesize and application of metal-oxide based bifunctional electrocatalysts with sustainability and efficient activity in water splitting is significant among the wide spread researches in energy applications. Herein, bifunctional electrocatalysts composed of NiFe₂O₄ dispersed on N-doped graphene has been prepared by in-situ polymerization and characterized for further bifunctional catalytic performances. The electrocatalyst exhibited bespoken performances as cathode in HER as well as anode in OER at alkaline electrolyte. The nanocomposite N-doped graphene/NiFe₂O₄ (NGNF) exhibited low overpotential of 184 mV in HER and 340 mV in OER for attaining the current density of 10 mA/cm² which is far better than their pristine counterparts. Similarly its Tafel slopes were found to be 82.9 mV/dec and 93.2 mV/dec for HER and OER. As an electrocatalyst NGNF outperformed pure nickel ferrite and graphene/NiFe₂O₄ (GNF) as bifunctional electrocatalyst with low overpotential and Tafel slopes. This indicates the impact of graphene and N-doping on graphene in the activity of pure NF. The graphene in the composite and the N-dopants provoked the catalytic activity and tuned the electron transfer and interaction with the electrolyte. Thus, herein we endow with strategies of preparing highly efficient bifunctional electrocatalysts by coupling spinel oxides and N-doped graphene for HER and OER.     

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

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

Effect of iron on Ni–Mo–Fe composite as a low-cost bifunctional electrocatalyst for overall water splitting

By increasing demand for hydrogen and oxygen gas for energy and industrial applications, designing a cheap, high-efficiency, and bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) seems necessary. For this purpose Ni–Mo–Fe as a bifunctional electrocatalyst was synthesized by one-step electrodeposition. From this electrocatalyst with optimal composition and current density, a small overpotential of 65, 161 mV for delivering 10, 100 mA/cm² on HER in alkaline media was achieved. As-fabricated electrode exhibited 344,408 mV for delivering 10, 100 mA/cm² in OER. Furthermore, this electrocatalyst shows high stability and negligible degradation in overpotential for HER and OER under long term stability tests in alkaline media. The notable function of As-fabricated Ni–Mo–Fe is due to the synergism effect between Ni, Mo, and Fe element and binder-free structure. Owing to the high-performance and high-stability of Ni–Mo–Fe electrocatalyst under Hydrogen and Oxygen evolution reactions is a candidate for industrial uses in the alkaline electrolyzer.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

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.     

Bimetallic metal-organic framework derived electrocatalyst for efficient overall water splitting

The development of bifunctional catalysts that can be applied to both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is widely regarded as a key factor in the production of sustainable hydrogen fuel by electrochemical water splitting. In this work, we present a high-performance electrocatalyst based on nickel-cobalt metal-organic frameworks for overall water splitting. The as-obtained catalyst shows low overpotential to reaches the current density of 10 mA cm⁻² with 249 mV for OER and 143 mV for HER in alkaline media, respectively. More importantly, when the electrolyzer was assembled with the as-prepared catalyst as anode and cathode simultaneously, it demonstrates excellent activity just applies a potential of 1.68 V to achieve 10 mA cm⁻² current density for overall water splitting.     

Facile synthesis of bimetallic Ni–Fe phosphide as robust electrocatalyst for oxygen evolution reaction in alkaline media

Bimetallic Ni–Fe phosphide electrocatalysts were in-situ synthesized through direct phosphorization of metal salts on carbon cloth (CC). The Fe dopant remarkably enhances the OER performance of Ni₂P in alkaline medium through the electronic structure modulation of Ni. The (Fe_0.5Ni_0.5)₂P/CC electrode, composed of uniform films coated on carbon fibers, delivers a low overpotential of 260 mV with a small Tafel slope of 45 mV·dec⁻¹ at the current density of 100 mA cm⁻², outperforming most reported non-noble electrocatalysts and commercial RuO₂ electrocatalyst. The (Fe_0.5Ni_0.5)₂P/CC also displays superior electrochemical stability at high current density. An appropriate Fe dopant level facilitates the in-situ transformation of Ni–Fe phosphides into active NiFeOOH during alkaline OER. This work simplifies the synthesis procedure of metal phosphides.     

Self-supported hierarchical porous FeNiCo-based amorphous alloys as high-efficiency bifunctional electrocatalysts toward overall water splitting

Rationally designing an efficient and cost-effective bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is a primary matter in applying electrocatalytic water splitting. Herein, a self-supported FeNiCo-based amorphous catalyst with a hierarchical micro/nanoporous structure is fabricated by dealloying an amorphous/nanocrystalline precursor. The amorphous nanoporous framework enables the prepared electrocatalyst to afford fast reaction kinetics, abundant active sites, and enhanced electrochemical active surface areas (ECSAs). Such structural advantages and the synergistic effects of the ternary transition metals contribute to a dramatic catalytic activity of this electrocatalyst under alkaline conditions, which delivers the current density of 10 mA cm⁻² at a low overpotential of 134 mV for HER and 206 mV for OER, respectively. Furthermore, a full electrolysis apparatus constructed by the self-supported hierarchical micro/nanoporous FeNiCo-based amorphous electrocatalyst as both cathode and anode acquires a dramatically low voltage of 1.58 V operating at 10 mA cm⁻² along with stability for more than 24 h for overall water splitting.     

Three-dimensional Ni/Fe doped graphene oxide @ MXene architecture as an efficient water splitting electrocatalyst

Developing a highly efficient, stable, and earth-abundant electrocatalyst for both HER and OER is essential for water splitting. Herein, we report a bifunctional electrocatalyst in the form of iron/nickel doped graphene oxide @ MXene (GMX). The GMX-based electrocatalytic materials were prepared by annealing at different temperatures in an inert atmosphere. The GMX was characterized by various analytical tools such as PXRD, FE-SEM, HRTEM, Raman spectroscopy, and XPS. All the electrocatalysts exhibit high activity when acting as OER and HER catalyst in alkaline and acidic electrolytes. GMX-500 is considered an effective bifunctional electrocatalyst, and 10 mA cm^?2 current density is achieved at a low overpotential, i.e., 370 mV for OER and 470 mV for HER, respectively. This paper focuses on the progress of inexpensive and effective electrocatalysts with high activity and long-term durability for water splitting, which is relevant in power conservation.     

Bifunctional electrocatalysts for water splitting from a bimetallic (V doped-NixFey) Metal–Organic framework MOF@Graphene oxide composite

An ongoing challenge still lies in the exploration of proficient electrocatalysts from earth-abundant non-precious metals instead of noble metal-based catalysts for clean hydrogen energy through large-Scale electrochemical water splitting. However, developing a non-precious transition metals based, stable electrocatalyst for cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) is important challenge for modern energy conversion technology. In this report Vanadium doped bimetallic nickel-iron nanoarray, fabricated by carbon supported architecture through carbonization process for electrochemical water splitting. Three types of catalysts were prepared in different molar ratio of Ni/Fe. The electrocatalytic performance demonstrated that the catalyst with equal mole ratio (0.06:0.06) of Ni/Fe possess high catalytic activity for both OER and HER in alkaline and acidic medium. Besides, our findings revealed that the doping of vanadium could play a strong synergetic effect with Ni/Fe, which provide a small overpotential of 90 mV and 210 mV at 10 mA cm^?2 for HER and OER respectively compared to the other two catalyst counterparts. Also, the catalyst with 1:1 (Ni/Fe) molar ratio showed a high current density of 208 mA cm^?2 for HER at 0.5 M H₂SO₄ and 579 mA cm^?2 for OER at 1 M KOH solution, the both current densities are much higher than the other two catalysts (different Ni/Fe ratio). In addition, the presented catalysts showed extremely good durability, reflecting in more than 20 h of consistent Chronoamprometry study at fixed overpotential η = 250 mV without any visible voltage elevation. Similarly, the (Ni/Fe) equal ratio catalyst showed better corrosion potential 0.209 V vs Ag/AgCl and lower current density 0.594 × 10^?12 A cm^?2 in high alkaline medium. The V-doping, MOF/GO surface defects are significantly increased the corrosion potential of the V-Ni_xFe_y-MOF/GO electrocatalyst. Besides, the water electrolyzed products were analysed by gas chromatography to get clear insights on the formed H₂ and O₂ products.     

Niobium-doped cobalt phosphide nanowires realizing enhanced electrocatalytic activity for overall water splitting

Designing cost-effective bifunctional catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline electrolyte remains a significant challenge. Herein, we report adding Nb to pristine CoP nanowires enhances the material's catalytic activities towards HER and OER. Density functional theory (DFT) calculation unravels that the Nb atoms not only optimize hydrogen binding abilities on CoP surface, but also modulate the surface electron densities of in situ formed β-CoOOH during anodic oxidation, thereby greatly accelerate both the HER and OER kinetics in alkaline solutions. In addition, an alkaline electrolyzer using Nb-doped CoP nanowires as cathode and anode for overall water splitting, delivers 100 mA cm^?2 at low cell voltage of 1.70 V, superior to Pt//RuO₂ couple. This doping strategy can be extended to other transition metal phosphides as multifunctional catalysts towards overall water splitting and beyond.     

Electrodeposition of Ni–Fe micro/nano urchin-like structure as an efficient electrocatalyst for overall water splitting

The usage of active electrocatalysts is a useful approach to accelerate the kinetics of electrochemical reactions and to enhance the efficiency of water splitting. To fabricate active electrocatalysts, the creation of new structures that can be easily constructed has always been a research interest. Ni–Fe based alloys are generally known as active OER catalyst. However, in this study, a novel Ni–Fe micro/nano urchin-like structure is reported to be active for both HER and OER. This is the first report of the fabrication of this morphology by a fast, one-step, and affordable electrodeposition method as an efficient HER/OER electrocatalyst. The optimized Ni–Fe coating on Cu substrate demonstrated promising HER activity with low overpotentials of ?124 and ?243 mV at the current densities of ?10 and ?100 mA cm^?2, respectively. Moreover, the fabricated Ni–Fe urchin-like catalyst is highly active toward OER, requiring overpotentials of only 292 and 374 mV to deliver 10 and 100 mA cm^?2. The unique structure of the synthesized coating with an abundant number of micro/nano-scale cones is suggested to play a vital role in the superior HER/OER activity of the catalyst. This article introduces a cost-effective method for the fabrication of a novel urchin-like Ni–Fe alloy as a highly active bifunctional water splitting electrocatalyst.     

Promotion of MXene (Ti3C2Tx) as a robust electrocatalyst for oxygen evolution reaction via active sites of ZIF-67 - In situ mechanism investigations

Developing a robust and highly efficient electrocatalyst for the oxygen evolution reaction (OER) is required, due to its sluggish mechanism and high overpotential. Here, we present the Ti₃C₂T_x and ZIF-67 composites (MXene/ZIF-67) for an efficient OER. The MXene/ZIF-67_1:10 exhibits an overpotential of 366 mV, which is better than MXene (548 mV) and RuO₂ (395 mV). Moreover, it shows improved electrochemical stability at 20 mA·cm^{− 2} with only a 0.2% increase in potential after 5 h, while RuO₂ with an overpotential loss of 3.5%. After an increase in the current density of 10–20 mA cm⁻² the potential increase by 7.4%, while in RuO₂ by 25.3%. To reveal the observed performance, the composite's robustness and explain each component's role. Moreover, a detailed OER mechanism is discussed. It was realized via in situ Raman microscopy and XRD which allowed the revealing of the active species responsible for boosting OER.     

Pomegranate-like Ni-doped cobalt boride implanted in B,N-doped carbon nanocages for enhanced electrochemical oxygen evolution

The development of efficient and stable transition metal boride electrocatalysts for oxygen evolution reaction (OER) is critical for energy conversion and environmental protection. Herein, we synthesized B, N-doped carbon layer encapsulated the Ni-doped Co_xB nanocages electrocatalyst (denoted as Ni-Co_xB@BNC) via a high-temperature boronizing, derived from Ni-doped cobalt-based zeolite imidazole frame (NiCo-ZIF), toward enhanced electrochemical alkaline oxygen evolution reaction. The Ni-Co_xB@BNC electrocatalyst synthesized at 550 °C exhibits excellent OER activity with a low overpotential of 274 mV and a Tafel slope of 80 mV dec⁻¹ at a current density of 10 mA cm⁻², which is better than precious metal RuO₂. The synergistic effect between B, N-doped carbon layer and Ni-doped Co_xB in Ni-Co_xB@BNC leads to higher OER catalytic activity. The B, N-doped carbon layer provides additional active sites, which accelerates charge transport and enhances the conductivity of Ni-Co_xB@BNC during OER. In addition, it also protects the pomegranate seed-like Ni-Co_xB nanoparticles inside, improving the stability of the Ni-Co_xB@BNC material. This work unambiguously elucidates the design and preparation strategy of transition metal boride implanted B, N-doped carbon nanocage electrocatalysts derived from controlled bimetallic ZIF precursor.