In situ surface dealumination of intermetallic NiFe aluminides electrocatalysts for enhancing the oxygen evolution

Herein, based on the mechanical alloying (MA) and in situ electrochemical etching methods, a series of porous Ni–Fe electrocatalysts with different Ni/Fe atomic ratios derived from intermetallic NiFe aluminides have been designed and applied to OER (oxygen evolution reaction) in alkaline solution. As comparing with bulk NiFe aluminides electrocatalyst, the porous electrocatalyst presents higher activity via the etching method. In addition, among all porous samples with different metal stoichiometric ratios, Ni_2/3Fe_1/3Al shows the highest OER activity with an overpotential of 299 mV at 10 mA cm^?2 and a Tafel slope of 58.9 mV dec^?1, which can be attributed to the high intrinsic activity and large electrochemical surface area from the leaching of Al. This work provides a promising route to in situ synthesize highly efficient electrocatalysts for water splitting.     

NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.     

NiFe single atom catalysts anchored on carbon for oxygen evolution reaction

Single atom catalysts (SACs) can improve the efficiency of oxygen evolution reaction (OER). However, metal SACs anchored on carbon materials are relatively uncommon for the OER. In this paper, using carbon black as carrier, NiFe SACs are fabricated by one step pyrolysis method. When the weight ratio of Ni/Fe is lower than 5:3, NiFe@C exibits highly-dispersed SACs over carbon in addition to some Ni₃Fe alloy. The prepared NiFe@C 5:3 SACs showed excellent OER performance with an overpotential of 322 mV and 438 mV for current density of 10 mA/cm² and 100 mA/cm², respectively. The Tafel slope of NiFe@C 5:3 was as small as 87.6 mV/dec, indicating fast charge transfer of NiFe@C 5:3 during OER process, which was also confirmed by electrochemical impedance spectra with R_ct = 18.07 Ωcm². Meanwhile, NiFe@C 5:3 had the highest specific capacitance of 5 mF/cm² with good stability. This work provides a reference for designing electocatalyst material for efficient, stable and economical OER process.     

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.     

Porous molybdenum carbide microspheres as efficient binder-free electrocatalysts for suspended hydrogen evolution reaction

Generally, the electrocatalysts are immobilized on conductive electrodes or in-situ grown on current-collecting substrates, which causes some disadvantages. For the first time, the obtained porous molybdenum carbide microspheres with diameters of 200–400 μm are employed as binder-free electrocatalysts in the novel model of suspended hydrogen evolution reaction (SHER), which possess the perfect catalytic stability and high practicability. Herein, porous molybdenum carbide microspheres synthesized by ion exchange reaction and subsequent calcining process are employed as electrocatalysts for HER, which possess a low onset potential of ?79 mV vs. RHE and a low overpotential of 174 mV achieving a current density of 10 mA/cm² in 0.5 M H₂SO₄. This work may provide a new methodology for rational design and fabrication of reaction pattern for the electrolysis of water.     

Mesoporous spinel NiFe oxide cubes as advanced electrocatalysts for oxygen evolution

Oxygen evolution reaction (OER) is the rate-controlling step of the electrochemical water splitting. The slow kinetics hinders large-scale H₂ production. Herein, the spinel NiFe oxides were prepared by directly pyrolyzing nickel hexacynoferrate precursors in air. The NiFe oxides were presented as mesoporous nanocubes with a specific surface area of 125 m² g⁻¹. The mesoporous spinel NiFe oxide nanocubes can afford a geometric current of 10 mA cm⁻² at a low overpotential of a 0.24 V and a small Tafel slope of 41 mV dec⁻¹ in alkaline solution. The specific activity can reach up to 0.37 mA cm⁻² with a turnover frequency of 0.93 s⁻¹. The superior OER activity of the NiFe oxide nanocubes (NiFeO NCs) can outperform those of the state-of-the-art IrO₂ catalysts, and compare favorably with other spinel transition metal oxides reported recently under identical condition. NiFeO NCs also show a long-term durability without significant loss of the OER activity. Our works provide a new strategy to develop efficient, robust and earth-abundant spinel NiFe oxides as advanced OER electrocatalysts to replace the expensive commercial IrO₂ catalysts for water splitting in the industrial scale.     

Hollow ZnxCo1-xSe2 microcubes derived from Metal–Organic framework as efficient bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions

Herein, we designed a simple and universal method to prepare cobalt-based bimetallic Zn_xCo_1-x-MOFs precursors, which were used as templates to synthesize effective bifunctional electrocatalyst hollow porous Zn_xCo_1-xSe₂ microcubes by one-step hydrothermal method. The cubic morphology of the Zn_xCo_1-x-MOFs precursors was well inherited. Particularly, the Zn_0.1Co_0.9Se₂ exhibited superior HER and OER performance in acidic solution and alkaline solution, respectively. Benefiting from the hollow porous structure, the synergistic effect of Zn–Co–Se and the incorporation of a small number of zinc atoms.

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NiFe layered double hydroxide nanosheet arrays for efficient oxygen evolution reaction in alkaline media

Exploring efficient oxygen evolution reaction (OER) catalysts synthesized from low-cost and earth-abundant elements are crucial to the progression of water splitting. In this paper, NiFe layered double hydroxide (LDH) nanosheets were grown on Ni foam (NF) through a straightforward hydrothermal method. The Fe doping effects were systematically investigated by controlling Ni/Fe ratios and Fe valence states, and the in-depth influence mechanisms were discussed. The results indicate that, through controlling structure morphology and enhancing Ni²⁺ oxidation, NiFe_III(1:1)-LDH displays the best and outstanding OER performance, with a low over potential of 382 mV at 50 mA cm^?2, a low Tafel slope of 31.1 mVdec^?1 and only 20 mV increase after 10 h continuous test at 50 mA cm^?2. To our knowledge, this is one of the best OER electrocatalysts in alkaline media to date. This work provides a facile and novel strategy for the fabrication of bimetallic LDH catalysts with desired structures and compositions.     

One-step gas phase sulfided NiFe coating as self-supporting electrode for high efficiency oxygen evolution reaction

The development of cost-effective oxygen evolution reaction (OER) electrocatalytic electrodes is one of the essential means of applying green hydrogen energy. Due to the complex steps in the anodic OER, the high overpotential hinders the kinetics of water splitting. In this paper, the sulfided NiFe coating was innovatively designed as a self-supporting OER electrode by high-velocity oxygen fuel (HVOF) spraying coupled with one-step gas phase sulfuration. The thickness of the NiFe coating is approximately 20 μm. After the sulfuration treatment, the surface of the NiFe coating is remolded into a uniform rock sugar-like structure, and simultaneously forms new NiS and Ni₃S₄ phases. The sulfided NiFe coating electrode shows relatively low overpotentials of 220 mV and 253 mV at the current density of 10 mA cm⁻² and 100 mA cm⁻², respectively, and the Tafel slope is as low as 28.6 mV dec⁻¹. The excellent electrocatalytic activity is mainly attributed to the synergistic effect of sulfides, the adsorption of OH⁻ by the Ni³⁺ in alkaline electrolyte, and the acceleration of O₂ separation by the S²⁻ through promoting the cleavage of O–O bonds. In addition, the sulfided NiFe coating electrode also has a small charge transfer resistance, and the potential stability is as high as 98.1% in the 70 h stability test. Therefore, the development of sulfided transition metal coating electrodes can provide a new idea for the large-scale industrialization of water splitting.     

Facile preparation of biomass-derived bifunctional electrocatalysts for oxygen reduction and evolution reactions

The development of inexpensive and efficient bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is still remained a challenge in wide range of renewable energy technologies. Herein, biomass-derived nitrogen self-doped porous carbon nanosheets (NPCNS) are produced by a facile and green pyrolysis of Euonymus japonicus leaves at controlled temperature and then the nitric acid pickling was carried out to remove the excess metal ingredients. The obtained NPCNS exhibits a hierarchically porous distribution, high BET surface area and uniform nitrogen doping. Electrochemical measurements show that the NPCNS possess a high electrocatalytic activity for both ORR and OER. Among these NPCNS catalysts, the sample carbonized at 900 °C (NPCNS-900) with the highest concentration of pyridinic nitrogen shows the best ORR and OER activity. According to our DFT calculations, the high content of pyridinic nitrogen with the moderate O and OH adsorption energies among the three types of nitrogen should be the critical factor for the efficient catalytic performance of NPCNS-900 toward ORR and OER. This work demonstrates that the facile prepared NPCNS-900 is a potential candidate material with excellent performance in electrocatalytic applications such as fuel cells or metal-air batteries.     

3D hierarchical network NiCo2S4 nanoflakes grown on Ni foam as efficient bifunctional electrocatalysts for both hydrogen and oxygen evolution reaction in alkaline solution

The development of cost-effective and high-efficiency electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) still remains highly challenging. Exposing as many active sites as possible is the key method to improve activity of HER and OER performance. In this communication, we demonstrate a novel 3D hierarchical network NiCo₂S₄ nanoflake grown on Ni foam (NiCo₂S₄-NF) as a highly efficient and stable electrochemical catalyst. The NiCo₂S₄-NF exhibits overpotentials as low as 289 and 409 mV at 100 mA cm^?2, superior long-term durability during a 20 h measurement, and a low Tafel slope of 89 and 91 mV dec^?1 for HER and OER in 1.0 M NaOH solution. The outstanding performance is owe to the inherent activity of ultrathin NiCo₂S₄ nanoflakes and the special structure of NiCo₂S₄-NF that can provide a huge number of exposed active sites, accelerate the transfer of electrons, and facilitate the diffusion of electrolyte simultaneously.     

Preparation of ultrathin molybdenum disulfide dispersed on graphene via cobalt doping: A bifunctional catalyst for hydrogen and oxygen evolution reaction

The development of highly active and low-cost catalysts for hydrogen evolution reaction (HER) is significant for the development of clean and renewable energy research. Owing to the low H adsorption free energy, molybdenum disulfide (MoS₂) is regarded as a promising candidate for HER, but it shows low activity for oxygen evolution reaction (OER). Herein, graphene-supported cobalt-doped ultrathin molybdenum disulfide (Co–MoS₂/rGO) was synthesized via a one-pot hydrothermal method. The obtained hybrids modified electrode exhibits a high HER catalytic activity with a low overpotential of 147 mV at the current density of 10 mA cm⁻², a small Tafel slope of 49.5 mV dec⁻¹, as well as good electrochemical stability in acidic electrolyte. Meanwhile, the catalyst shows remarkable OER activity with a low overpotential of 347 mV at 10 mA cm⁻². The superior activity is ascribed not only to the high conductivity originated from the reduced graphene, but also to the synergistic effect between MoS₂ and cobalt.     

Defective layered NiFe double hydroxides anchored on self-supported CoNi-nitrogen doped carbon nanotube composite as advanced electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is an essential process during electrochemical water-splitting. Due to its sluggish kinetics, low cost and highly efficient catalyst is invariably desired to decrease its overpotential for large-scale application. However, the overpotential of most advanced OER electrocatalysts is still more than 200 mV at the current density of 10 mA cm^?2. In this work, we constructed active layered NiFe double hydroxides with cation defects on self-supported three-dimensional (3D) CoNi nitrogen-doped carbon nanotube composite substrate as integrated OER catalyst. Strikingly, electrochemical measurements showed that the optimized sample exhibited outstanding OER activity with low overpotentials of 178 and 268 mV at the current densities of 10 and 100 mA cm^?2 in alkaline environment, alongside a good durability. The excellent OER performance was ascribed to the strongly synergistic effect of intrinsically active NiFe double hydroxide layers with abundant cation vacancies and 3D carbon nanotube composite substrate with good conductivity and various functional moieties, thus facilitating the electrocatalytic kinetic.     

Porous and wrinkle treatment of commercial Ni foam and its application for high-efficiency oxygen evolution reaction electrode

Exploring high-efficiency electrode for oxygen evolution reaction (OER) is critically important toward the water splitting. In this article, we put forward a novel and facile approach, oxidation and subsequent reduction, for in situ porous and wrinkled treatment of commercial nickel foam to construct a micron rough nickel foam (MRNF). The fabricated MRNF is developed as a current collector to construct an OER composite electrode by depositing nanostructured Co(OH)₂ on its surface via constant voltage deposition method. The results indicate that the porous and wrinkled treatment could obviously increases the contact sites between current collector (MRNF) and active material (Co(OH)₂), leading to a remarkably reduction in charge transfer resistance. The designed MRNF/Co(OH)₂ electrode presents enhanced OER electrocatalysis activity with a low overpotential of 274.4 mV at the current density of 10 mA cm^?2 within alkaline solution. Furthermore, the hierarchical porous and wrinkle structures of the MRNF also significantly improve the mechanical integrity of the electrode, resulting in superior stability.     

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.     

Trimetallic PdCuIr nanocages as efficient bifunctional electrocatalysts for polyalcohol oxidation and hydrogen evolution reaction

Despite amounts of researches in recent years, it is still desirable but challenging to fabricate well-defined bifunctional catalysts with high performance towards alcohol oxidation and hydrogen evolution reaction (HER). Herein, a unique trimetallic PdCuIr catalyst with a nanocage (NC) structure is synthesized to be an excellent bifunctional catalyst by a seed-mediated growth strategy. The as-prepared PdCuIr NC catalyst exhibits remarkably enhanced mass activity and durability towards glycerol oxidation reaction (GOR) and ethylene glycol oxidation reaction (EGOR) as compared with commercial Pd/C catalyst. The optimal Pd₅₈Cu₃₂Ir₁₀ NCs show electrocatalytic activities of 2565.79 mA mg_Pd⁻¹ and 4498.30 mA mg_Pd⁻¹ for GOR and EGOR, respectively. Meanwhile, the well-defined PdCuIr NC catalyst also displays outstanding electrocatalytic performance for HER, and the overpotential of Pd₅₈Cu₃₂Ir₁₀ NCs only requires 54 mV to arrive at a current density of 10 mA cm⁻², along with excellent electrochemical durability. The enhancement of electrocatalytic properties is attributed to the introduction of Cu and Ir atoms, which could modify the electronic structure of Pd to optimize the adsorption of reactants and intermediates. Moreover, the unique NC structure also significantly increases the number of reaction active sites as well as accelerates mass transport. Following this method, the trimetallic PdCuRu NCs and PdCuRh NCs are also synthesized. This work not only offers a general strategy for the fabrication of well-defined ternary alloy nanocatalysts, but also presents an advanced class of bifunctional catalysts for polyalcohol electrooxidation and HER.     

Co-Magneli phases electrocatalysts for hydrogen/oxygen evolution

The subject of this work is the use of non-stoichiometric titanium oxides – Magneli phases as support material of Co-based electrocatalysts aimed for hydrogen/oxygen evolution reaction. Commercial micro-scaled Ebonex (Altraverda, UK) was mechanically treated for 4, 8, 12, 16 and 20 h and further Co metallic phase was grafted by sol-gel method. Morphology of Co/Ebonex electrocatalysts was observed by means of TEM and SEM microscopy, while electrochemical behavior by means of cyclic voltammetry and steady-state galvanostatic method.     

Se-doped cobalt oxide nanoparticle as highly-efficient electrocatalyst for oxygen evolution reaction

Electrolysis of water has been one of the most promising approaches for renewable energy resources while the efficient oxygen evolution reaction (OER) remains challenging. Herein, a series of different ratio of Se doped Co₃O₄ nanoparticles XSe-Co₃O₄ are prepared by hydrothermal method and applied as OER electrocatalysts. Se^2? is doped into the Co₃O₄ crystal lattice by substituting of O^2? and a large number of oxygen vacancies are generated, which provides more available activity sites for OER. Se doping increases the surface ratio of Co²⁺/Co³⁺ and accelerates the electron transport that favors OER activity promotion. The optimized doping ratio of 6%Se–Co₃O₄ presents low overpotential of 281 mV at 10 mA cm^?2, as well as a low Tafel slope of 70 mV dec^?1 in 1 M KOH solution, which has great advantages compared to the recently reported Co₃O₄-based OER electrocatalysts. This work provides new ideas for the development of efficient Co₃O₄-based OER electrocatalysts.     

Cu-doped GdFeO3 perovskites as electrocatalysts for the oxygen evolution reaction in alkaline media

Development of electrocatalysts for the oxygen evolution reaction (OER) plays a critical role in electrochemical water splitting systems. In this aim, iron based perovskite oxides with composition GdFe_1-x Cu_x O₃ (0 ≤ x ≤ 0.3) have been investigated. The effect of copper doping, calcination temperature on the OER performance in alkaline media was studied. The incorporation of Cu²⁺ (0 ≤ x ≤ 0.3) decreases the activity of calcined electrodes at 800 °C from 6.33 to 2.79 mA cm⁻², while that containing 0.2 mol of copper calcined at 600 °C, exhibits the higher activity (9.66 mA cm⁻²) at 0.66 V. The stability study during 8 h indicates that the undoped electrode calcined at 800 °C, exhibits relatively a better stability of the OER performance compared to that doped with 20% of copper calcined at 600 °C. The achieved results show promising potential for cost-effective hydrogen generation using earth-abundant materials and cheap fabrication processes.     

NiOx nanoparticles supported on polyethylenimine functionalized CNTs as efficient electrocatalysts for supercapacitor and oxygen evolution reaction

Ni oxide based nanoparticles (NPs) have been widely used as electrocatalysts in the electrochemical energy storage and conversion applications. In this paper, NiO_x NPs are successfully synthesized by the self-assembly of Ni precursor onto polyethylenimine functionalized carbon nanotubes (PEI-CNTs) assisted with microwave radiation. NiO_x NPs with size around 2–3 nm are homogenously dispersed on the PEI-CNTs supports with no aggregation. The electrochemical activity of NiO_x NPs on PEI-CNTs, NiO_x/PEI-CNTs, as effective electrocatalysts is studied for supercapacitor and oxygen evolution reaction in alkaline solutions. NiO_x/PEI-CNTs show a capacitance of 1728 and 1576 F g⁻¹ based on active material, and 221 and 394 F g⁻¹ based on total catalyst loading on 12.5% and 25% NiO_x/PEI-CNTs, respectively, which is substantially higher than 152 F g⁻¹ of unsupported NiO. The NiO_x/PEI-CNTs electrodes exhibit reversible and stale capacitance of ∼1200 F g⁻¹ based on active materials after 2000 cycles at a high current density of 10 A g⁻¹. NiO_x/PEI-CNTs also exhibit significantly higher activities for oxygen evolution reaction (OER) of water electrolysis, achieving a current density of 100 A g⁻¹ at an overpotential of 0.35 V for 25% NiO_x/PEI-CNTs. It is believed that the uniformly dispersed nano-sized NiO_x NPs and synergistic effect between the NiO_x NPs and PEI-CNTs is attributed to the high electrocatalytic performance of NiO_x/PEI-CNTs electrocatalysts. The results demonstrate that NiO_x NPs supported on PEI-CNTs are highly effective electrocatalysts for electrochemical energy storage and conversion applications.