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.     

N,S co-doped NiCo2O4@CoMoO4/NF hierarchical heterostructure as an efficient bifunctional electrocatalyst for overall water splitting

Electrocatalytic overall water splitting technology has received considerable attention in recent years. The fabrication of low-cost, earth-rich and potent bifunctional electrocatalysts is vital for hydrogen evolution (HER) and oxygen evolution reactions (OER). Herein, the N and S co-doped NiCo₂O₄@CoMoO₄ heterostructures (N, S–NCO@CMO₄₀₀) are fabricated by CVD and hydrothermal methods. N and S atoms as auxiliary active centers can increase the activity of Ni, Co and Mo atoms at the same time. Hierarchical heterostructures generate more interfaces to accelerate mass transfer and enlarge the electrochemical surface area, which greatly enhances the catalytic activity. The catalyst displays outstanding OER performance. The overpotentials of OER and HER are 165 and 100 mV at a current density of 10 mA cm^?2, respectively. More importantly, the N, S–NCO@CMO₄₀₀-based water splitting cell has a low voltage of 1.46 V at 10 mA cm^?2. Furthermore, the N, S–NCO@CMO₄₀₀ runs for 120 h in stable operation. This work provides new ideas for the design of hierarchical heterostructures with two-element incorporation.     

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.     

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.     

Mo/P doped NiFeSe as bifunctional electrocatalysts for overall water splitting

Designing high-efficiency catalysts for overall water splitting is critical to reduce the cost of hydrogen fuel as a clean and renewable energy source in future society. In this work, a Mo-, P-codoped NiFeSe was successfully synthesized on nickel foam (NF) by one-step electrodeposition. Through the doping strategy, the conductivity can be well promoted, and the production of nanosheets on the catalyst surface and active phases during hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) provided much more active sites, which leaded to efficient HER/OER performances of as-synthesized Mo-, P-codoped NiFeSe catalysts, i.e., a low overpotential of 100 mV/200 mV at current density of 10 mA cm⁻² in 1.0 M KOH with stability of 95 h/60 h, respectively. It only required 1.53 V to deliver a current density of 10 mA cm⁻² in overall water splitting and maintained outstanding durability for 100 h. This work is beneficial to future design of high efficient and low-cost bifunctional catalysts for overall water splitting.     

Nickel sulfide-based electrocatalysts for overall water splitting

Hydrogen is a green energy with sustainability and high energy density. Electrochemical water splitting (EWS) is a promising green strategy for hydrogen production. Noble metal electrocatalysts exhibit excellent electrocatalytic activity in EWS. However, the applications of noble metals in EWS are limited because of their scarcity and high price. Therefore, the research on non-noble metal electrocatalysts has attracted much attention. Among them, nickel sulfide electrocatalysts, with a unique 3D structure, pretty conductivity, and adjustable electronic structure, show significant electrocatalytic activity in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this review, the mechanism of the electrocatalytic reaction, electrochemical parameters, and preparation methods of nickel sulfide are introduced first. Then, the five methods including atomic doping (including cations, anions and diatoms), morphological control, hybridization, integration with nanocarbon, and high-index facets exposure to regulate the electronic structure and active sites of nickel sulfide were illustrated, so as to improve the electrocatalytic activity of nickel sulfide. The electrocatalytic properties of these nickel sulfides were reviewed. However, there are some problems in the research of electrocatalysis, such as how to further improve the conductivity of the electrocatalyst, and the calculation method of current density is not unified. Therefore, our future development direction is to prepare a stable nickel sulfide electrocatalyst, study relevant strategies to simultaneously increase active sites and improve conductivity, and effectively make nickel sulfide into an EWS catalyst with higher performance.     

Integrating Co3O4 nanoparticles with MnO2 nanosheets as bifunctional electrocatalysts for water splitting

Developing high-efficiency and low-cost electrocatalyst is significant for the application of water splitting technology. Herein, Co₃O₄ nanoparticles and MnO₂ nanosheets are separately synthesized and subsequently assembled into a unique 0/2-dimensional heterostructure via van der Waals interactions. The consequent composites expose abundant accessible active sites and expedite the reaction kinetics, which can be testified by the superiorities in Tafel slope, exchange current density and double-layer capacitance, only requiring overpotentials of 355 and 129 mV for oxygen and hydrogen evolution reactions in 1.0 M KOH at 10 mA cm^?2, respectively. Moreover, a cell voltage of 1.660 V can drive the electrolyzer at 10 mA cm^?2. Benefitted from robust integration, the original aggregation and restacking of individual materials have been overcome, thereby leading to superior elelctrocatalysis durability. This facile and universal strategy may inspire the researchers on the design and construction of advanced functional composites.     

Graphene-based electrocatalysts: Hydrogen evolution reactions and overall water splitting

Recently, carbon-based materials (e.g., graphene, carbon nanotubes, carbon quantum dots) have been used as electrocatalysts to catalyze the reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Among them, graphene has attracted attention as an electrocatalyst, and its electrocatalytic performances have been improved by doping with metals and non-metals, surface and defect engineering, and hybrid development. In this perspective, the present paper reviewed the recent advances (2018 onwards) on the progress of graphene-based electrocatalysts for HER and overall water splitting (OWS). It is emphasizing strategies for optimizing electrocatalytic properties followed by challenges and future outlook. This review will provide the essential ideas and strategies that can help design graphene-based electrocatalysts of high performance that can be implemented for sustainable energy application.     

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.     

Dysprosium doped copper oxide (Cu1-xDyxO) nanoparticles enabled bifunctional electrode for overall water splitting

The production of hydrogen, a favourable alternative to an unsustainable fossil fuel remains as a significant hurdle with the pertaining challenge in the design of proficient, highly productive and sustainable electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, the dysprosium (Dy) doped copper oxide (Cu_1-xDy_xO) nanoparticles were synthesized via solution combustion technique and utilized as a non-noble metal based bi-functional electrocatalyst for overall water splitting. Due to the improved surface to volume ratio and conductivity, the optimized Cu_1-xDy_xO (x = 0.01, 0.02) electrocatalysts exhibited impressive HER and OER performance respectively in 1 M KOH delivering a current density of 10 mAcm^?2 at a potential of ?0.18 V vs RHE for HER and 1.53 V vs RHE for OER. Moreover, the Dy doped CuO electrocatalyst used as a bi-functional catalyst for overall water splitting achieved a potential of 1.56 V at a current density 10 mAcm^?2 and relatively high current density of 66 mAcm^?2 at a peak potential of 2 V. A long term stability of 24 h was achieved for a cell voltage of 2.2 V at a constant current density of 30 mAcm^?2 with only 10% of the initial current loss. This showcases the accumulative opportunity of dysprosium as a dopant in CuO nanoparticles for fabricating a highly effective and low-cost bi-functional electrocatalyst for overall water splitting.     

Low Ir-content Ir/Fe@NCNT bifunctional catalyst for efficient water splitting

In order to reduce the cost of electrocatalysts and increase the exposure of the Ir active sites while ensuring the stability of the catalyst, a N-doped carbon nanotube (NCNT) is applied as a conductive support to confine the Ir clusters for avoiding them growing up via a modified method based on pyrolysis of a mixture of melamine, ferric chloride and iridium trichloride. It is found that Ir species in the as-obtained Ir(20)/Fe@NCNT-900 composite exist in two forms, Ir nanoclusters (1–2 nm) dotted on the wall of NCNT and the Ir atomically scattered on the Fe nanoparticles wrapped in the NCNT. Although the Ir content of Ir(20)/Fe@NCNT-900 is extremely low (～4 wt% Ir), the composite catalyst delivers excellent activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) with an exceptionally low overpotential of 4.7 mV/11 mV for HER and 300 mV/270 mV for OER to drive 10 mA cm^?2 in 0.5 M H₂SO₄/1.0 M KOH electrolyte respectively, which exceeds the commercial Pt/C (20 wt% Pt) and IrO₂ benchmarks. In addition, it has much higher mass activity for OER at 1.55 V (1.78 A mg^?1_Ir) than those of the referenced catalysts in acid. The cell voltage of the two-electrode system assembled by Ir(20)/Fe@NCNT-900 for total water splitting in acidic and alkaline media are only 1.520 V and 1.510 V to afford 10 mA cm^?2 separately, lower than that of Pt/C||IrO₂ and with a good stability. Our work provides a construction method of low-content precious metal composite catalysts which can be applied in OER and overall water splitting field.     

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.     

Study of cobalt boride-derived electrocatalysts for overall water splitting

The production of clean hydrogen fuel by the electrolysis of water requires highly active, low-cost and facilely prepared electrocatalyst that minimizes energy consumption. Here we report an active cobalt boride (CoB)-derived electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The CoB catalyst can be readily deposed on 3D nickel foam (NF) using a simple electroless plating method. A comprehensive analysis of the CoB catalyst with scanning electron microscopy transmission (SEM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) techniques revealed that CoOOH is formed on the surface of CoB catalyst during the OER process and Co(OH)₂ is formed in the HER process. The catalyst derived from CoB/NF exhibits low overpotentials towards both OER and HER in alkaline solution. The electrolysis cell using the CoB-derived catalyst couple requires a cell voltage of 1.69 V to afford a current density of 10 mA/cm², which compares favorably with most non-noble bifunctional electrocatalysts. The favorable combination of high-performance, low cost and facile preparation suggests that transition metal borides may act as promising electrocatalyst for water splitting.     

Template-free synthesis of 1D hollow Fe doped CoP nanoneedles as highly activity electrocatalysts for overall water splitting

Development of low cost and high efficiency electrocatalysts for water splitting systems to produce renewable hydrogen energy is still a significant requirement. The engineering of nanostructure and element doping are effective methods to further improve the performance of catalysts. Nonmetal (such as N, P, S) doping has been extensively investigated, while the report of metal doping is relatively few. Herein, Fe doped CoP 1D hollow nanoneedles on carbon cloth (CC) are designed and fabricated by a hydrothermal method and subsequent phosphorization procedure. The conversion of Fe doped Co-hydroxide@CC to Fe–CoP can produce large number of nanopores, which are closely connected to each other, and form hollow structures within the nanoneedles. Benefiting from the effective Fe doping and the particular hollow nanoneedle structure, the obtained Fe–CoP@CC demonstrates good electrocatalytic activity for hydrogen evolution reaction (HER) both in alkaline and acidic solution, affording a current density of 10 mA cm⁻² at overpotential of 49 mV and 80 mV, respectively. Moreover, the two-electrode electrolyzer with Fe–CoP@CC as both the cathode and anode catalyst achieve a current density of 10 mA cm⁻² at a cell voltage of 1.58 V in 1.0 M KOH solution. The results illustrate that the obtained hollow Fe–CoP@CC nanoneedles can serve as an efficient catalyst for overall water splitting.     

Graphitic-polytriaminopyrimidine (g-PTAP): A novel bifunctional catalyst for photoelectrochemical water splitting

In this study, an electrode of g-PTAP, a novel bifunctional catalyst for photoelectrochemical was fabricated and utilized for water splitting. The graphitic-poly (2,4,6-triaminopyrimidine (g-PTAP) was synthesized by the thermal vapor condensation polymerization (TVCP) method on FTO glass. The structure, morphology, and optical characteristics of the resultant g-PTAP were analyzed using analytical techniques such as FT-IR, Raman, XRD, XPS, CHNS, FE-SEM, EDS, and DRS. The synthesized g-PTAP was graphitic with sheet-like morphology and revealed maximum light absorbance capacity in the visible range. The DFT calculation showed an appropriate HOMO-LUMO band position for overall water splitting which was verified experimentally for H₂ and O₂ generation at photocathode and photoanode, respectively. Moreover, the g-PTAP sample exhibited good photo-stability as a photocathode as compared to a photoanode. This work can provide a pathway for fabricating highly efficient semiconductor photocatalyst for overall water splitting and solar energy such as conversion.     

Electrodeposited nickel–iron–carbon–molybdenum film as efficient bifunctional electrocatalyst for overall water splitting in alkaline solution

Designing and synthesizing of efficient and inexpensive bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is one of the current research topics. In this study, NiFeCMo film in nickel mesh substrate is prepared by one-step direct-current electrodeposition method. The obtained NiFeCMo film shows the excellent electrocatalytic activity, which only requires overpotentials of 254 mV for HER and 256 mV for OER to drive current density of 10 mA cm⁻², with corresponding Tafel slopes of 163.9 and 60.3 mV·dec⁻¹ in 30% KOH medium, respectively. Moreover, NiFeCMo film only needs a low cell voltage of 1.61 V to drive current density of 10 mA cm⁻² in an alkaline electrolyzer. Such remarkably HER and OER properties of NiFeCMo alloy is attributed to the increased effective electrochemically active surface area and the synergy effect among Ni, Fe, C and Mo.     

Metal organic frameworks as electrocatalysts: Hydrogen evolution reactions and overall water splitting

The development of clean energy technologies to protect the environment is an important demand of the times. Electrocatalysis is emerging as a promising method for evolution of hydrogen and overall water splitting. Nowadays, metal organic frameworks (MOFs) have emerged as electrocatalysts having uniformly distributed active sites and high electrical conductivity. This review summarizes the latest advances in heterogeneous catalysis by MOFs and their composite/derivatives for efficient hydrogen evolution reaction (HER) and water splitting. Pristine MOFs with their recent development are summarized first followed by composites of MOFs with their enhanced electrocatalytic performances. Overall water splitting by using bifunctional electrocatalysts derived from MOFs with different synthetic approaches is provided and this review gives the metal-based categorisation of precursor MOFs. Different strategies to improve chemical stability, conductivity, and overall electrocatalytic properties have been discussed. In the last, perspectives on the synthesis of efficient MOF-based electrocatalyst materials are provided.     

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.     

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.     

NiA and NiX zeolites as bifunctional electrocatalysts for water splitting in alkaline media

NiA and NiX zeolites were prepared and characterised using XRD, FTIR and SEM, and subsequently tested as electrodes for hydrogen (HER) and oxygen (OER) evolution reactions in alkaline media. Linear sweep voltammetry and chronoamperometry techniques showed that NiA has higher catalytic activity for these two reactions, as evidenced by higher current densities, which can be correlated with a higher weight fraction of Ni in this electrocatalyst than in the NiX and with its higher conductivity. HER and OER kinetic parameters, including Tafel slope, exchange current density and apparent activation energy were evaluated. Electrochemical impedance spectroscopy analysis yielded values of the resistance of the solution, charge transfer and mass transfer, as well as double layer capacitance and pseudo-capacitance of the working electrode, at different potentials and temperatures. Unlike the HER, during which the mass transfer resistance of the adsorbed intermediate is dominant in the case of NiA, the OER impedance response is controlled by the charge transfer process itself at the potentials of interest for these process. The overall resistance related to the HER is lower for NiA than for NiX.