Controlled synthesis of NiCo2O4@Ni-MOF on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction

Heterostructured materials with special interfaces and features give a unique character for much electrocatalytic process. In this work, the introduction of exogenous modifier Ni-MOF improved the reaction kinetics and morphology of the NiCo₂O₄@Ni-MOF/NF catalyst. As-obtained NiCo₂O₄@Ni-MOF/NF has excellent oxygen evolution reaction (OER) performance and urea oxidation reaction (UOR) performance. The catalyst need overpotential of 340 mV at a current density of 100 mA cm^?2 for OER and a potential of 1.31 V at the same current density for UOR. The Tafel slopes of NiCo₂O₄@Ni-MOF/NF is 38.34 and 15.33 mV dec^?1 for OER and UOR respectively, which is more superior than 78.58 and 66.73 mV dec^?1 of NiCo₂O₄/NF. The nanosheets microstructure is beneficial to the adsorption and transport of electrolyte and the presence of a large number of mesoporous channels can also accelerate gas release, and then improves activity of the catalyst. Density functional theory calculation demonstrate that NiCo₂O₄ plays a role in absorbing water, while the existence of in situ generated NiOOH can promote the electron transfer efficiency. It is synergies of NiCo₂O₄ and in situ generated NiOOH that enhance the decomposition of water on the surface of the NiCo₂O₄@Ni-MOF/NF. This investigation provides a new strategy for the application of spinel oxide and MOF materials.     

Synthesis of high crystalline nickel‐iron hydrotalcite‐like compound as an efficient electrocatalyst for oxygen evolution reaction

The nickel‐iron hydroxide‐like catalyst for oxygen evolution reaction (OER) is prepared by an improved coprecipitation method. The crystallization degree of hydrotalcite‐like compound is high, and the lamellar structure is homogeneous with no agglomeration, which helps to build efficient mass‐transfer layer channel of OH^? ions. The NiFe layered double hydroxide (LDH)/carbon nanotubes (CNTs) electrode shows good performance and stability for OER. The potential of NiFe LDH/CNTs electrode is only 0.592 V (vs HgO/Hg) at 200 mA·cm^?2 in 6 mol·L^?1 potassium hydroxide (KOH) electrolyte, which shows excellent catalytic activity for OER. The NiFe LDH/CNTs electrode works continuously for 620 hours at 200 mA·cm^?2, with the groove voltage only rises 0.1 V.     

Low-pressure-plasma-processed NiFe-MOFs/nickel foam as an efficient electrocatalyst for oxygen evolution reaction

A NiFe bimetallic metal organic framework (MOF) deposited on nickel foam and processed by low-pressure plasmas with 95%Ar+5%H₂, pure Ar, and 95%Ar+5%O₂ gases is used as an electrocatalyst for the oxygen evolution reaction. An alkaline solution (1 M KOH) with 95%Ar+5%H₂ plasma processed NiFe-MOFs/NF exhibits the best electrocatalytic performance with the lowest overpotential of 149 mV at a current density of 10 mA cm^?2 and a Tafel slope of 54 mV dec^?1. Furthermore, electrical impedance spectroscopy and cyclic voltammetry show that after 95%Ar+5%H₂ plasma treatment, the interfacial impedance greatly reduces, and the electrical double-layer capacitance slightly increased.     

Amine group ligand-modified hydrotalcite-like nano cobalt hydroxide for efficient oxygen evolution reaction

The advancement of highly-efficient, non-noble metal electrocatalysts with high active sites for oxygen evolution reaction (OER) continues to face severe challenges. In this work, a new 3D flower-like α-Co(OH)₂ catalyst with high Co–NH₂ active sites (referred to as α-Co(OH)₂–NH₂) is prepared. The Co–NH₂ active sites are formed through the interactions between Co²⁺ and –NH₂ groups and exhibit higher electrocatalytic performance for OER in alkaline mediums, with a lower overpotential (300 mV at 10 mA cm⁻²), a flatter Tafel slope (75 mV dec⁻¹) and a longer stability. Moreover, water splitting catalyzed by α-Co(OH)₂–NH₂ delivers 1.62 V to reach a current density of 10 mA cm⁻². The mechanism studies show that the OER electrocatalytic activity is closely related to the content of –NH₂. Density functional theory (DFT) calculations unveil that –NH₂ groups can facilitate the formation of OH1 on the α-Co(OH)₂ surface and promote the desorption of O₂1 into O_2(g).     

Template assisted hydrothermal synthesis of CoSnO3 hollow microspheres for electrocatalytic oxygen evolution reaction

The practical complications suffered by the most recognized electrochemical energy systems, such as, water-electrolyzers and metal-air batteries reside in the half-cell oxygen evolution reaction. To resolve this problem, continuous colossal efforts are required to develop the active, affordable and sustainable electrocatalysts. Shape-tailoring of the catalysts, constructed from non-noble metals is one of the emerging strategies to augment the activity of the material toward electrochemical reactions. In the present work, we demonstrate the template-assisted hydrothermal synthesis of hierarchical CoSnO₃ hollow microspheres, constructible from the wafer-thin sheets of CoSnO₃. The hierarchical CoSnO₃ hollow microspheres possess a high specific surface area of 153.59 m²/g, and mesoporous configuration, which are the essential pre-requisites of an electrochemical system. In addition to this, the proposed CoSnO₃ hollow microspheres possess adequate electroactive surface area (793.5 cm²) and happens to be a suitable candidate for driving the oxygen evolution reaction with a low overpotential of 282 mV and Tafel slope of 96.5 mV/dec in alkaline medium. The higher turnover frequency (0.0045 s⁻¹), high specific and mass activities (2.195 mA/cm²_EASA and 28.752 mA/mg, respectively) were observed for CoSnO₃ hollow spheres. Furthermore, the chronoamperometric measurement reveals a good stability of CoSnO₃ hollow microspheres in alkaline condition, satisfying the fundamental demand of an energy system.     

Fe/Ni bimetallic organic framework with varying anions as robust electrocatalyst for oxygen evolution reaction

The performance of the metal?organic frameworks (MOFs) will be affected when the anions added were different. Herein, bimetallic FeNi-MOF was synthesized by hydrothermal method with nickel foam as substrate, the effects of four anions (Cl^?, NO₃^?, CH₃COO^?, SO₄^2?) on the materials performance of MOF were investigated. The MOF prepared when added chloride ion with the overpotential at 100 mA?cm^?2 as 247 mV. Meanwhile, the stability test at 100 mA cm^?2 for 12 h had no obvious change which exhibited high electrochemical stability. The analysis demonstrated that the superior performance of the MOF prepared when added chloride ion was attributed to the low charge transfer resistance, increased active area, exposure more active sites. This work would shed some lights for facile synthesis of ultrahigh performance OER catalyst by adjusting the anion of the precursor.     

Fe7Se8@Fe2O3 heterostructure nanosheets as bifunctional electrocatalyst for urea electrolysis

Water electrolysis for producing hydrogen is considered to be the most feasible means to develop new green energy. Compared with above, urea electrolysis can improve energy conversion efficiency by introducing urea, and can also be used for purification of wastewater rich in urea. In this paper, a bifunctional electrocatalyst with heterostructure, namely Fe₇Se₈@Fe₂O₃ nanosheets supported on nickel foam, were synthesized for the first time through typical hydrothermal and partial oxidation processes. Iron cation promotes electron transfer and adjusts electron structure under the synergistic action of selenium and oxygen anion, thus achieving excellent catalytic activity of urea electrolysis. In an alkaline solution of 1 M KOH with 0.5 M urea, the Fe₇Se₈@Fe₂O₃/NF catalyst can drive the current density of 10 mA cm^?2 with requiring only potential of 1.313 V and overpotential of 141 mV for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), respectively. What is noteworthy is that Fe₇Se₈@Fe₂O₃/NF heterostructure is used as bifunctional electrocatalyst to form urea electrolyzer device, which only needs potential of 1.55 V to drive current density of 10 mA cm^?2, which is one of the best catalytic activities reported so far, and the electrode couple showed remarkable stability for 15 h. Density functional theory shows that the Fe₇Se₈@Fe₂O₃/NF material exhibits the minimum Gibbs free energy for the adsorption of hydrogen. This work provides a new method for exploring novel and environmentally friendly bifunctional electrocatalysts for urea electrolysis.     

Self-supported Ni3S2@MoS2 core/shell nanorod arrays via decoration with CoS as a highly active and efficient electrocatalyst for hydrogen evolution and oxygen evolution reactions

A hierarchically porous MoS₂ on Ni₃S₂ nanorod array on Ni foam (MoS₂/Ni₃S₂/NF) was firstly fabricated through a simple microwave-assisted hydrothermal method, and then followed by electrochemical deposition approach in which MoS₂/Ni₃S₂/Ni foam is decorated with CoS (CoSMoS₂/Ni₃S₂/NF). In contrast to conventional hydrothermal approach, microwave irradiation accelerates the synthesis of MoS₂/Ni₃S₂/Ni foam from time of >20 h–2 h. The characterization of CoSMoS₂/Ni₃S₂/NF by scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM) indicate that a whole scale of 1D the Ni₃S₂ nanorods were hierarchically integrated with MoS₂ and CoS nanosheets. The as-synthesized CoSMoS₂/Ni₃S₂/NF hybrid not only endows the ease transport of electrons along Ni₃S₂ nanorods to Ni foam, but also accommodates maximal exposure of active edge sites to the reactants through hierarchically porous CoS doped MoS₂ nanosheets, accomplishing the promoted kinetics and activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). By electrochemical measurements such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscope (EIS), we find that the CoSMoS₂/Ni₃S₂/NF hybrid shows markedly enhanced electrochemical performance for both HER and OER. Specifically, the optimal CoSMoS₂/Ni₃S₂/NF8C possesses the low overpotentials (η₁₀) of 85 and 225 mV at current density (|j|) of 10 mA cm^?2 in 1.0 M KOH and the small 62.3 and 46.1 mV dec^?1 Tafel slope for HER and OER, respectively, outperforming those of most of the current noble metal-free electrocatalysts. These results highlight the fact that CoSMoS₂/Ni₃S₂/NF is a high-performance, noble-metal-free electro-catalyst, and provide a potential avenue toward achieving an enhanced electrocatalytic activity towards both in HER and OER. Yet the duration of the as prepared catalyst in OER still need to be improved.     

Boron doped cryptomelane as a highly efficient electrocatalyst for the oxygen evolution reaction

In this study, cryptomelane-type (1D) MnO₂ was doped with boron powder by ball-milling in an inert organic solvent under various experimental conditions. The structural, thermal, morphological, and surface features of samples prepared by the ball-milling method were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and surface measurements. The electrocatalytic oxygen evolution reaction (OER) performances of the samples were tested and compared with the bare cryptomelane to reveal the effect of boron doping into manganese oxide. It was found that boron particles transformed to trigonal BO₃ units in the cryptomelane structure via mechanical activation, and accordingly, the oxidation state of manganese in this structure relatively changed. The 0.25% B-doped cryptomelane sample prepared at 12 h grinding time exhibited the overpotential of 425 mV at a current density of 1 mAcm⁻² with a Tafel slope of ∼95 mV dec⁻¹. It showed a remarkable catalytic performance among the other electrocatalysts under neutral pH compared to bare cryptomelane. When the elemental boron doping exceeded 1%, the electrochemical performance dramatically decreased depending on the blocking of the Mn³⁺ active sites.     

Ir-doped Co3O4 as efficient electrocatalyst for acidic oxygen evolution reaction

Oxygen evolution reaction (OER) is an important bottleneck for large-scale acidic water splitting applications due to its sluggish reaction kinetics. Therefore, the development of highly active, stable, and inexpensive electrocatalysts for OER remains a challenge. Herein, we develop the iridium doped Co₃O₄ (Ir–Co₃O₄) with low Ir content of 2.88 wt% for efficient acidic OER. Considering systemic characterizations, it is probably concluded that Ir can be uniformly doped into the lattice of Co₃O₄ and induce a certain distortion. The electrochemical results reveal that Ir–Co₃O₄ nanoparticles demonstrate significantly enhanced electrocatalytic OER activity and stability in 0.5 M H₂SO₄ solution compared with pure Co₃O₄, in which the overpotential at the current density of 10 mA cm⁻² decreases from 382 mV to 225 mV and the value of Tafel slope decreases from 101.7 mV dec⁻¹ to 64.1 mV dec⁻¹. Besides, Ir–Co₃O₄ exhibits excellent electrocatalytic durability for continuous 130 h's test without any activity attenuation. Moreover, this work provides a kind of high-performance acidic OER electrocatalyst for the development of hydrogen energy.     

Three-demensional NiCoNiCo2O4/NF as an efficient electrode for hydrogen evolution reaction

At present, there is an urgent need for plentiful non-noble metal catalyst to substitute for valuableness platinum based metal catalyst in electrochemical water splitting. Here, we fabricated a three-demensional (3D) NiCoNiCo₂O₄ nanosheets electrocatalyst that directly grew on Ni foam firstly and then were reduced in 0.1 mol dm⁻³ sodium borohydride solution. This electrode exhibited high activity in 1.0 mol dm⁻³ KOH solution with an onset potential of ∼40 mV and a tafel slope of 77 mV dec⁻¹. Furthermore, the NiCoNiCo₂O₄/NF electrode showed a splendid durability during long-playing electrochemical test. Our work may provide an inexpensive, easy-to-obtain and excellent catalyst candidate for future electrolytic water research and industry studies that may involve hydrogen applications in the future.     

Novel one-step synthesis of nickel encapsulated carbon nanotubes as efficient electrocatalyst for hydrogen evolution reaction

In this work, we report the synthesis of Ni nanoparticles encapsulated in carbon nanotubes (CNTs) by a facile and novel one-step pyrolysis method which are obtained from fumaric acid and nickel acetate as carbon and nickel sources respectively. The synthesized Ni encapsulated CNTs were characterized by various methods and were confirmed to possess large surface areas and numerous mesopores, they were applied as non-precious metal electrocatalyst for HER in 1 M KOH solution. The results show that the Ni encapsulated carbon nanotubes synthesized at 650 °C exhibited the best catalytic activity and stability with the smallest Tafel slope of 102 mV dec⁻¹, an onset potential of 110 mV and overpotential of 266 mV to achieve a current density of −10 mA cm⁻².     

One‐pot synthesis of Pd‐MoO2/C by microwave sintering as an efficient electrocatalyst for ethanol oxidation reaction

The composite catalysts of Pd‐MoO₂/C for ethanol oxidation reaction (EOR) were prepared by microwave sintering. MoO₃ was thermally reduced to MoO₂ by carbon black in the preparing process of the Pd‐MoO₂/C material. The TEM analysis showed that Pd‐MoO₂ was well polymerized. Chronoamperometric, cyclic voltammetry, and electrochemical impedance spectra methods were applied to reveal the performance for EOR at room temperature. The Pd‐MoO₂/C electrode exhibited considerable high activity and stability. MoO₂ as a co‐catalyst significantly improved the catalytic activity of Pd‐MoO₂/C for EOR.     

Fe2O3-encapsulated and Fe-Nx-containing hierarchical porous carbon spheres as efficient electrocatalyst for oxygen reduction reaction

It is highly desirable to develop high-efficiency non-precious electrocatalysts toward oxygen reduction reaction (ORR). In this work, Fe₂O₃-encapsulated and Fe-Nx-containing porous carbon spheres (Fe₂O₃/N-MCCS) with unique multi-cage structures and high specific surface area (1360 m² g^?1) are fabricated. The unique porous structure of Fe₂O₃/N-MCCS ensures fast transportation of oxygen during ORR. The combined effect of Fe₂O₃ nanoparticles and Fe-Nx configurations endows Fe₂O₃/N-MCCS (E_1/2 = 0.837 V vs. RHE) with superior ORR activity and methanol tolerance to Pt/C. And, Fe₂O₃/N-MCCS exhibits better stability than nitrogen-modified carbon. The characterization results of Fe₂O₃/N-MCCS after long-term test reveals its excellent structural stability. Impressively, zinc-air battery based on Fe₂O₃/N-MCCS showed a peak power density of 132.4 mW cm^?2 and a specific capacity of 797 mAh g^?1, respectively.     

Mixed-metal MOF-derived Co-doped Ni3C/Ni NPs embedded in carbon matrix as an efficient electrocatalyst for oxygen evolution reaction

The exploration of electrocatalysts with high oxygen evolution reaction (OER) activity is highly desirable and remains a significant challenge. Transition metal carbides (TMCs) have been investigated as remarkable hydrogen evolution reaction (HER) electrocatalysts but few used as oxygen evolution reaction (OER) electrocatalysts. Herein, a Co doped Ni₃C/Ni uniformly dispersed in a graphitic carbon matrix was prepared by pyrolysis of a metal organic framework (Co/Ni-MOF) under a flow of Ar/H₂ at 350 °C, and Ni₃C/Ni@C was also prepared for comparison. The various characterization techniques confirmed the successful preparation of the heteroatom doped TMCs-based catalysts by pyrolysis of MOFs. Co doped Ni₃C/Ni@C exhibited superior electrocatalytic properties for OER. For example, Co–Ni₃C/Ni@C depicts a lower overpotential and smaller Tafel slope than Ni₃C/Ni@C and IrO₂ during the OER in 1 M KOH solution, additionally, it shows a higher active surface area than Ni₃C/Ni@C. The outstanding electrocatalytic performance of Co-doped Ni₃C/Ni@C in the OER was mainly ascribed to the synergistic effect of the Co and Ni₃C/Ni active sites.     

Spinel NiCo2O4 3-D nanoflowers supported on graphene nanosheets as efficient electrocatalyst for oxygen evolution reaction

Efficient oxygen evolution reaction (OER) electrocatalysts with non-noble metals are very critical for the large-scale exploitation of electrocatalytic hydrogen production systems. To improve the catalytic activity of OER electrocatalysts, several design strategies, such as construction of nanostructures, porous structures and composite materials have been proposed. Herein, spinel NiCo₂O₄ 3-D nanoflowers supported on graphene nanosheets (GNs) are prepared by a simple solvothermal synthesis method as non-noble metal electrocatalysts for OER. The present NiCo₂O₄/GNs composite integrates multiple advantages of nanostructures, porous structures and composite materials, including high surface area, abundant catalytic sites and high stability. Benefiting from the favorable features, the NiCo₂O₄/GNs composite exhibits a better OER performance than NiCo₂O₄ and RuO₂ in alkaline medium, which has a low onset potential (1.50 V), a small Tafel slope (137 mV dec⁻¹). The present work opens a new window for the construction of the carbon-supported 3-D nanostructure of transition metal catalysts with optimizable electrocatalytic performances for electrocatalytic hydrogen production.     

Development of RuO2/CeO2 heterostructure as an efficient OER electrocatalyst for alkaline water splitting

Here, the synthesis of RuO₂ loaded CeO₂ with varying amount of Ru loading with enhanced amount of Ce³⁺ and surface area, through synthesis of CeO₂ using cerium ammonium carbonate complex as procure followed by Ru loading by impregnation and calcination at 300 °C, is presented. Corresponding characterizations by XRD, SEM, TEM, XPS of all the samples reveal the formation of highly crystalline mesoporous CeO₂ nanoparticles with uniformly dispersed RuO₂ particles on the CeO₂ surface having approximately 45% Ce³⁺. All the samples were utilized as oxygen evolution reaction (OER) catalyst for electrocatalytic H₂ generation through water electrolysis. Electrocatalytic experiments reveal that synthesized 1 wt% RuO₂ loaded CeO₂ (1-RuO₂/CeO₂) showed superior OER activity. A quite low over-potential of 350 mV is required to attain a current density of 10 mA/cm² (ɳ₁₀), with a Tafel slope of 74 mVdec⁻¹ for OER in 1 M KOH solution. The synthesized 1-RuO₂/CeO₂ electrocatalyst also exhibited superior long term stability in basic medium and redox atmosphere.     

Reduced CoFe2O4/graphene composite with rich oxygen vacancies as a high efficient electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is regarded as a limit-efficiency process in electrochemical water splitting generally, which needs to develop the effective and low-cost non-noble metal electrocatalysts. Oxygen vacancies have been verified to be beneficial to enhance the electrocatalytic performance of catalysts. Herein, we report the facile synthesis of reduced CoFe₂O₄/graphene (r-CFO/rGO) composite with rich oxygen vacancies by a citric acid assisted sol-gel method, heat treatment process and the sodium borohydride (NaBH₄) reduction. The introduction of graphene and freezing dry technique prevents the restacking of GO and the aggregation of CFO nanoparticles (NPs) and increases the electronic conductivity of the catalyst. Fast heating rate and low anneal temperature favors to obtain low crystallinity and lattice defects for CFO. NaBH₄ reduction treatment further creates the rich oxygen vacancies and electrocatalytic active sites. The obtained r-CFO/rGO with high specific surface area (108 m² g⁻¹), low crystallinity and rich oxygen vacancies demonstrates a superior electrocatalytic activity with the smaller Tafel slope (68 mV dec⁻¹), lower overpotential (300 mV) at the current density of 10 mA cm⁻², and higher durability compared with the commercial RuO₂ catalyst. This green, low-cost method can be extended to fabricate similar composites with rich defects for wide applications.     

Controlled synthesis of CrxPy-a/ComPn-b nanoarray on nickel foam as efficient electrocatalyst for overall urea splitting

Developing highly efficient bifunctional urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) catalysts for urea splitting to hydrogen are one of the strategies to cope with the energy crisis. Here, a series of Cr_xP_y-a/Co_mP_n-b composites were synthesized on Ni foam through hydrothermal and low-temperature phosphorization process for the first time. It is worth noting that Cr_xP_y-1/Co_mP_n-3@NF exhibited excellent UOR performance (1.331 V at 100 mA cm^?2) and HER performance (0.299 V at 100 mA cm^?2) in an electrolyte of 1 M KOH and 0.5 M urea due to the synergistic effect of Cr–Co. The Cr_xP_y-1/Co_mP_n-3@NF||Cr_xP_y-1/Co_mP_n-3@NF two-electrode system call for only 1.52 V to provide current density of 10 mA cm^?2, which is one of the best electrochemistry performances reported up to now. Experimental analysis show that the promoted electrochemistry performances is assigned to faster charge transfer rate, the exposure of more reaction site and better properties of metals. Density Functional theory (DFT) results demonstrate that the presence of the Co_mP_n material accelerates the kinetics of hydrogen production and the Cr_xP_y material improves the properties of metals for the electrode. The work provides a new idea to develop the environmentally friendly and low cost overall urea splitting catalyst with transition metals instead of noble metals.     

One-pot synthesis of PdZnO/C by microwave sintering method as an efficient electro catalyst for ethanol oxidation reaction

The PdZnO/C catalytic material for ethanol oxidation reaction is prepared by microwave heating-glycol reduction method. PdZnO is well polymerized and dispersed on XC72. The results demonstrate that PdZnO/C has better electro catalytic activity and stability for ethanol oxidation reaction than Pd/C at room temperature. ZnO/C shows no catalysis for ethanol oxidation. The oxidation peak potential of PdZnO/C electrode is shifted negatively to 0.21 V. The current density of PdZnO/C electrode is 145 mA cm⁻², while that of the Pd/C electrode is 60 mA cm⁻². Moreover, single cell discharge test shows that discharge voltage of the PdZnO/C electrode reaches to 0.41 V at 30 mA cm⁻². In summary, ZnO as a co-catalyst significantly improves the activity of PdZnO/C catalyst for ethanol oxidation reaction.