Hollow Nanotube Ru/Cu2+1O Supported on Copper Foam as a Bifunctional Catalyst for Overall Water Splitting

Hydrogen energy is considered as one of the ideal clean energies for solving the energy shortage and environmental issues, and developing highly efficient electrocatalysts for overall water splitting to produce hydrogen is still a huge challenge. Herein, for the first time, Ru-doped Cu₂₊₁O vertically arranged nanotube arrays in situ grown on Cu foam (Ru/Cu₂₊₁O NT/CuF) are reported and further investigated for their catalytic properties for overall water splitting. The Ru/Cu₂₊₁O NT/CuF presents ultrahigh catalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline conditions, and it exhibits a small overpotential of 32 mV at 10 mA cm⁻² in the HER, and only needs 210 mV overpotential to achieve a current density of 10 mA cm⁻² in the OER. Importantly, the alkaline electrolyzer using Ru/Cu₂₊₁O NT/CuF as a bifunctional electrocatalyst only needs 1.53 V voltage to deliver a current density of 10 mA cm⁻², which is much lower than the benchmark of IrO₂(+)/Pt(−) counterpart (1.64 V at 10 mA cm⁻²). The excellent performance of the Ru/Cu₂₊₁O NT/CuF catalyst is attributed to its high conductive substrate and special Ru-doped nanotube structure, which provides a high electrochemical active surface area and 3D gas diffusion channel.     

Heterostructured Inter-Doped Ruthenium–Cobalt Oxide Hollow Nanosheet Arrays for Highly Efficient Overall Water Splitting

The development of transition-metal-oxides (TMOs)-based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter-doped ruthenium–cobalt oxide [(Ru–Co)O_x] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)O_x nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm⁻² and a small Tafel slope of 23.5 mV dec⁻¹, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm⁻². As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm⁻² for alkaline overall water splitting.     

Fabrication of a Hierarchical Ni(OH)2@Ni3S2/Ni Foam Electrode from a Prussian Blue Analogue-Based Composite with Enhanced Electrochemical Capacitive and Electrocatalytic Properties

Developing high-efficiency, cost-effective, and durable electrodes is significant for electrochemical capacitors and electrocatalysis. Herein, a 3D bifunctional electrode consisting of nickel hydroxide nanosheets@nickel sulfide nanocubes arrays on Ni foam (Ni(OH)₂@Ni₃S₂/NF) obtained from a Prussian blue analogue-based precursor is reported. The 3D higher-order porous structure and synergistic effect of different compositions endow the electrode with large specific surface area, facile ion/electron transport path, and improved conductivity. As a result, the Ni(OH)₂@Ni₃S₂/NF electrode exhibits a high specific capacity of 211 mA h g⁻¹ at a current density of 1 A g⁻¹ and 73 % capacity retention after 5000 cycles at 5 A g⁻¹. Moreover, the Ni(OH)₂@Ni₃S₂/NF electrode has superior electrocatalytic activity for the hydrogen evolution reaction with low overpotentials of 140 and 210 mV at current densities of 10 and 100 mA cm⁻², respectively. The synthetic strategy for the unique higher-order porous structure can be extended to fabricate other composite materials for energy storage and conversion.     

Magnetic NiFe2O4 Nanoparticles Prepared via Non-Aqueous Microwave-Assisted Synthesis for Application in Electrocatalytic Water Oxidation

Phase-pure spinel-type magnetic nickel ferrite (NiFe₂O₄) nanocrystals in the size range of 4 to 11 nm were successfully synthesized by a fast and energy-saving microwave-assisted approach. Size and accessible surface areas can be tuned precisely by the reaction parameters. Our results highlight the correlation between size, degree of inversion, and magnetic characteristics of NiFe₂O₄ nanoparticles, which enables fine-tuning of these parameters for a particular application without changing the elemental composition. Moreover, the application potential of the synthesized powders for the electrocatalytic oxygen evolution reaction in alkaline media was demonstrated, showing that a low degree of inversion is beneficial for the overall performance. The most active sample reaches an overpotential of 380 mV for water oxidation at 10 mA cm⁻² and 38.8 mA cm⁻² at 1.7 V vs. RHE, combined with a low Tafel slope of 63 mV dec⁻¹.     

Manganese-Modulated Cobalt-Based Layered Double Hydroxide Grown on Nickel Foam with 1D–2D–3D Heterostructure for Highly Efficient Oxygen Evolution Reaction and Urea Oxidation Reaction

Hydrogen production by energy-efficient water electrolysis is a green avenue for the development of contemporary society. However, the oxygen evolution reaction (OER) and the urea oxidation reaction (UOR) occurring at the anode are impeded by the sluggish reaction kinetics during the water-splitting process. Consequently, it is promising to develop bifunctional anodic electrocatalysts consisting of nonprecious metals. Herein, a bifunctional CoMn layered double hydroxide (LDH) was grown on nickel foam (NF) with a 1D–2D–3D hierarchical structure for efficient OER and UOR performance in alkaline solution. Owing to the significant synergistic effect of Mn doping and heterostructure engineering, the obtained Co₁Mn₁ LDH/NF exhibits satisfactory OER activity with a low potential of 1.515 V to attain 10 mA cm⁻². Besides, the potential of the Co₁Mn₁ LDH/NF catalyst for UOR at the same current density is only 1.326 V, which is much lower than those of its counterparts and most reported electrocatalysts. An urea electrolytic cell with a Co₁Mn₁ LDH/NF anode and a Pt–C/NF cathode was established, and a low cell voltage of 1.354 V at 10 mA cm⁻² was acquired. The optimized strategy may result in promising candidates for developing a new generation of bifunctional electrocatalysts for clean energy production.     

Heterostructured Inter‐Doped Ruthenium–Cobalt Oxide Hollow Nanosheet Arrays for Highly Efficient Overall Water Splitting

The development of transition‐metal‐oxides (TMOs)‐based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter‐doped ruthenium–cobalt oxide [(Ru–Co)O_x] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)O_x nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm^?2 and a small Tafel slope of 23.5 mV dec^?1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm^?2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm^?2 for alkaline overall water splitting.     

NixCo3‐xO4 Nanoneedle Arrays Grown on Ni Foam as an Efficient Bifunctional Electrocatalyst for Full Water Splitting

Developing highly active, stable and robust electrocatalysts based on earth‐abundant elements for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is important for many renewable energy conversion processes. Herein, Ni_xCo_3‐xO₄ nanoneedle arrays grown on 3D porous nickel foam (NF) was synthesized as a bifunctional electrocatalyst with OER and HER activity for full water splitting. Benefiting from the advantageous structure, the composite exhibits superior OER activity with an overpotential of 320 mV achieving the current density of 10 mA cm^?2. An exceptional HER activity is also acquired with an overpotential of 170 mV at the current density of 10 mA cm^?2. Furthermore, the catalyst also shows the superior activity and stability for 20 h when used in the overall water splitting cell. Thus, the hierarchical 3D structure composed of the 1D nanoneedle structure in Ni_xCo_3‐xO₄/NF represents an avenue to design and develop highly active and bifunctional electrocatalysts for promising energy conversion.     

Ru-Doping Enhanced Electrocatalysis of Metal–Organic Framework Nanosheets toward Overall Water Splitting

An Ru-doping strategy is reported to substantially improve both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalytic activity of Ni/Fe-based metal–organic framework (MOF) for overall water splitting. As-synthesized Ru-doped Ni/Fe MIL-53 MOF nanosheets grown on nickel foam (MIL-53(Ru-NiFe)@NF) afford HER and OER current density of 50 mA cm⁻² at an overpotential of 62 and 210 mV, respectively, in alkaline solution with a nominal Ru loading of ≈110 μg cm⁻². When using as both anodic and cathodic (pre-)catalyst, MIL-53(Ru-NiFe)@NF enables overall water splitting at a current density of 50 mA cm⁻² for a cell voltage of 1.6 V without iR compensation, which is much superior to state-of-the-art RuO₂-Pt/C-based electrolyzer. It is discovered that the Ru-doping considerably modulates the growth of MOF to form thin nanosheets, and enhances the intrinsic HER electrocatalytic activity by accelerating the sluggish Volmer step and improving the intermediate oxygen adsorption for increased OER catalytic activity.     

Interfacial Engineering FeOOH/CoO Nanoneedle Array for Efficient Overall Water Splitting Driven by Solar Energy

Interface engineering has been applied as an effective strategy to boost the electrocatalytic performance because of the strong coupling and synergistic effects between individual components. Here, we engineered vertically aligned FeOOH/CoO nanoneedle array with a synergistic interface between FeOOH and CoO on Ni foam (NF) by a simple impregnation method. The synthesized FeOOH/CoO exhibits outstanding electrocatalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. For the overall water splitting, the bifunctional FeOOH/CoO nanoneedle catalyst requires only a cell voltage of 1.58 V to achieve a current density of 10 mA cm⁻², which is much lower than that required for IrO₂//Pt/C (1.68 V). The FeOOH/CoO catalyst has been successfully applied for solar cell-driven water electrolysis, revealing its great potential for commercial hydrogen production and solar energy storage.     

Co3O4@Cu-Based Conductive Metal–Organic Framework Core–Shell Nanowire Electrocatalysts Enable Efficient Low-Overall-Potential Water Splitting

In the work reported herein, the electrocatalytic properties of Co₃O₄ in hydrogen and oxygen evolution reactions have been significantly enhanced by coating a shell layer of a copper-based metal–organic framework on Co₃O₄ porous nanowire arrays and using the products as high-performance bifunctional electrocatalysts for overall water splitting. The coating of the copper-based metal–organic framework resulted in the hybridization of the copper-embedded protective carbon shell layer with Co₃O₄ to create a strong Cu−O−Co bonding interaction for efficient hydrogen adsorption. The hybridization also led to electronically induced oxygen defects and nitrogen doping to effectively enhance the electrical conductivity of Co₃O₄. The optimal as-prepared core–shell hybrid material displayed excellent overall-water-splitting catalytic activity that required overall voltages of 1.45 and 1.57 V to reach onset and a current density of 10 mA cm⁻², respectively. This is the first report to highlight the relevance of hybridizing MOF-based co-catalysts to boost the electrocatalytic performance of nonprecious transition-metal oxides.     

Controlled Synthesis of 3D Flower‐like Ni2P Composed of Mesoporous Nanoplates for Overall Water Splitting

Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni₂P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Ni_x P_y , the 3D flower‐like Ni₂P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H₂SO₄, with a small Tafel slope of 79 mV dec⁻¹ and an overpotential of about 240 mV at a current density of 10 mA cm⁻² with a mass loading density of 0.283 mg cm⁻². In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm⁻² and a small Tafel slope of 72 mV dec⁻¹. The excellent catalytic performance of the as‐prepared Ni₂P may be ascribed to its novel 3D morphology with unique mesoporous structure.     

Tuning the Composition and Structure of Ni@MoC Nanosheets for Highly Active and Stable Electrocatalysis in Water Splitting

The conventional electrolytic water-splitting process for hydrogen production is plagued by high energy consumption, low efficiency, and the requirement of expensive catalysts. Therefore, finding effective, affordable, and stable catalysts to drive this reaction is urgently needed. We report a nanosheet catalyst composed of carbon nanotubes encapsulated with MoC/Mo₂C, the Ni@MoC-700 nanosheet showcases low overpotentials of 275 mV for the oxygen evolution reaction and 173 mV for the hydrogen evolution reaction at a current density of 10 mA ⋅ cm⁻². Particularly noteworthy is its outstanding performance in a two-electrode system, where a cell potential of merely 1.64 V is sufficient to achieve the desired current density of 10 mA ⋅ cm⁻². Furthermore, the catalyst demonstrates exceptional durability, maintaining its activity over a continuous operation of 40 hours with only minimal attenuation in overpotential. These outstanding activity levels and long-term stability unequivocally highlight the promising potential of the Ni@MoC-700 catalyst for large-scale water-splitting applications.     

A Supramolecular Coordination-Polymer-Derived Electrocatalyst for the Oxygen Evolution Reaction

An iron oxide decorated nickel iron alloy nanoparticle/porous graphene hybrid exhibits high electrocatalytic activity and excellent durability toward oxygen evolution reaction (OER). It displays a low overpotential of 274 mV at 10 mA cm⁻², and low Tafel slope of 37 mV dec⁻¹, showing a superior performance to the state-of-the-art RuO₂ OER electrocatalyst.     

Coupling Magnetic Single-Crystal Co2Mo3O8 with Ultrathin Nitrogen-Rich Carbon Layer for Oxygen Evolution Reaction

Transition-metal oxides as electrocatalysts for the oxygen evolution reaction (OER) provide a promising route to face the energy and environmental crisis issues. Although palmeirite oxide A₂Mo₃O₈ as OER catalyst has been explored, the correlation between its active sites (tetrahedral or octahedral) and OER performance has been elusive. Now, magnetic Co₂Mo₃O₈@NC-800 composed of highly crystallized Co₂Mo₃O₈ nanosheets and ultrathin N-rich carbon layer is shown to be an efficient OER catalyst. The catalyst exhibits favorable performance with an overpotential of 331 mV@10 mA cm⁻² and 422 mV@40 mA cm⁻², and a full water-splitting electrolyzer with it as anode catalyst shows a cell voltage of 1.67 V@10 mA cm⁻² in alkaline. Combined HAADFSTEM, magnetic, and computational results show that factors influencing the OER performance can be attributed to the tetrahedral Co sites (high spin, t₂³e⁴), which improve the OER kinetics of rate-determining step to form *OOH.     

Filling the Charge–Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material

The high charge–discharge voltage gap is one of the main bottlenecks of zinc–air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo₂O_4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by Mn^IV-induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge–discharge voltage gap (0.43 V at 10 mA cm⁻²) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal–air batteries.     

Accelerating H2 Evolution by Anodic Semi-dehydrogenation of Tetrahydroisoquinolines in Water over Co3O4 Nanoribbon Arrays Decorated Nickel Foam

Coupling the H₂ evolution reaction in water with thermodynamically favorable organic oxidation reactions is highly desirable, because it can enhance the energy conversion efficiency compared with electrocatalytic water splitting, and produce value-added chemicals instead of O₂ in the anodic reaction. Herein, Co₃O₄ nanoribbon arrays in situ grown on nickel foam (Co₃O₄@NF) was employed as an effective electrocatalyst for the selective oxidation of tetrahydroisoquinolines (THIQs). Various value-added semi-dehydrogenation products including dihydroisoquinolines with electro-deficient or -rich groups could be obtained with moderate yields and faradaic efficiencies. Benefitting from the rich surface active sites of Co₃O₄@NF, a two-electrode (Co₃O₄@NF||Pt) electrolytic system drove a benchmark current density of 10 mA cm⁻² at a cell voltage as low as 1.446 V in 1.0 M KOH aqueous solution containing 0.02 M THIQ, which was reduced by 174 mV in comparison with that of overall water splitting.     

Synthesis of a Hierarchically Porous C/Co3O4 Nanostructure with Boron Doping for Oxygen Evolution Reaction

Fabricating a low‐cost and highly efficient electrocatalyst is of importance for the development of renewable energy devices. In this work, we have synthesized an ultrafine cobalt oxide nanocatalyst (5–10 nm) doped with boron (BC/Co₃O₄) by using a metal–organic framework as a precursor, which exhibits an excellent catalytic activity for oxygen evolution reaction (OER). Owing to the improvement of accessible active sites by boron doping, the synthesized catalyst can reach a current density of 10 mA cm^?2 at 1.54 V with a low overpotential of 310 mV, superior than those of commercial RuO₂ and N‐doped C/Co₃O₄. This work provides a facile way to develop highly efficient catalysts for electrochemical reactions.     

Atmospheric-Temperature Chain Reaction towards Ultrathin Non-Crystal-Phase Construction for Highly Efficient Water Splitting

Combining the self-sacrifice of a highly crystalline substance to design a multistep chain reaction towards ultrathin active-layer construction for high-performance water splitting with atmospheric-temperature conditions and an environmentally benign aqueous environment is extremely intriguing and full of challenges. Here, taking cobalt carbonate hydroxides (CCHs) as the initial crystalline material, we choose the Lewis acid metal salt of Fe(NO₃)₃ to induce an aqueous-phase chain reaction generating free CO₃²⁻ ions with subsequent instant FeCO₃ hydrolysis. The resultant ultrathin (∼5 nm) amorphous Fe-based hydroxide layer on CCH results in considerable activity in catalyzing the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), yielding 10/50 mA ⋅ cm⁻² at overpotentials of 230/266.5 mV for OER and 72.5/197.5 mV for HER. The catalysts can operate constantly in 1.0 M KOH over 48 and 45 h for the OER and HER, respectively. For bifunctional catalysis for alkaline electrolyzer assembly, a cell voltage as low as 1.53 V was necessary to yield 10 mA cm⁻² (1.7 V at 50 mA cm⁻²). This work rationally builds high-efficiency electrochemical bifunctional water-splitting catalysts and offers a trial in establishing a controllable nanolevel ultrathin lattice disorder layer through an atmospheric-temperature chemical route.     

PtM/MxBy (M=Ni,Co, Fe) Heterostructured Nanobundles as Advanced Electrocatalyst for Hydrogen Evolution Reaction

Optimizing the electronic and synergistic effect of hybrid electrocatalysts based on Pt and Pt-based nanocatalysts is of tremendous importance towards a superior hydrogen evolution performance under both acidic and alkaline conditions. However, developing an ideal Pt-based hydrogen evolution reaction (HER) electrocatalyst with moderated electronic structure as well as strong synergistic effect is still a challenge. Herein, we fabricated boron (B)-doped PtNi nanobundles by a two-step method using NaBH₄ as the boron source to obtain PtNi/Ni₄B₃ heterostructures with well-defined nanointerfaces between PtNi and Ni₄B₃, achieving an enhanced catalytic HER performance. Especially, the PtNi/Ni₄B₃ nanobundles (PtNi/Ni₄B₃ NBs) can deliver a current density of 10 mA cm⁻² at the overpotential of 14.6 and 26.5 mV under alkaline and acidic media, respectively, as well as outstanding electrochemical stability over 40 h at the current density of 10 mA cm⁻². Remarkably, this approach is also universal for the syntheses of PtCo/Co₃B and PtFe/Fe₄₉B with outstanding electrocatalytic HER performance.     

Cooperative Ni(Co)-Ru-P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self-powered H2 Production

Water electrolysis for H₂ production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru₁−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm⁻², respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm⁻² at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru₁−NiCoP optimize H* adsorption, and enhance adsorption of *N₂H₂ to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H₂ production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h⁻¹ m⁻².