Recent Progress on Nickel-Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed.     

Identification by Electron Probe Microbeam Analysis of Submicron Borides in Joints of Nickel Base Superalloys

The phases formed at the interface between an intermetallic (NiAl) and a nickel base superalloy joined by combustion synthesis were investigated, particularly the eutectic phases. Owing to their small size, the characterisation of these phases using a Castaings electron microprobe encounters difficulties. The analysis volume size is generally too large to differentiate the phases from their surrounding matrix, even by using low accelerating voltage. Moreover, the eutectic phases contain boron, which is difficult to characterise by EPMA. Independently of the phases shape, the characterisation can be solved by viewing this complex system as a surrounding matrix and a multi layer system. The results of these simulations revealed the presence of two categories of borides: the eutectic boride MM₂B₂ (M=Mo and M=Co, Cr) and the solid solution boride [Cr_1–x (Mo, W)_x]B.     

Size-controllable carbon spheres doped Ni (II) for enhancing the catalytic oxidation of methanol

Ni(II)/CSs were prepared using a simple two-step hydrothermal method. The morphology and composition of the catalysts were studied with scanning electron microscope, transmission electron microscope, and X-ray diffraction. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy showed that the surface of the prepared carbon spheres was rich in hydroxyl groups, which was beneficial to remove CO intermediates, and therefore, improving the catalytic efficiency and the antipoisoning ability of the catalysts. The results of cyclic voltammetry and chronoamperometry showed that the electrocatalytic activity and stability of Ni(II)/CSs were higher than that of unloaded NiAc under alkaline environment. When the nickel content was 5 wt.%, the peak oxidation current density of methanol on Ni(II)/CSs electrocatalyst reached the maximum of 34.54 mA/cm², which was about 1.8 times that of unloaded NiAc. These results indicate that Ni(II)/CSs has potential applications in the electrocatalytic oxidation of methanol.     

Theoretical investigation of the crystallographic structure,anisotropic elastic response,and electronic properties of the major borides in Ni-based superalloys

ABSTRACT

In Ni-based superalloys, it is usually found that borides can strengthen the grain boundaries, thereby resulting in an increase in mechanical strength and high-temperature creep properties. Due to their importance and prevalence in Ni-based superalloys, this study employs first-principles methods to investigate the crystallographic structure, anisotropic elastic response, and electronic properties of the major borides, such as M₂B, M₅B₃ and M₃B₂ (M: Cr, Mo, W), respectively, which is necessary for the assessment of complex mechanical responses of Ni-based superalloys. The results demonstrate that the studied borides are all thermodynamically and mechanically stable. Among the M _x B _y binary borides analysed, Cr _x B _y exhibits the largest shear modulus, Young’s modulus, and Vicker hardness values, and these properties increase with the increase of B contents. The studied borides display nearly isotropic elastic properties except for W₅B₃ and W₃B₂. The electronic structure analysis of M _x B _y shows that the strong hybridisation between M-d and B-p orbitals leads to these borides exhibiting higher theoretical hardness, and the overlapping peaks of M-d and B-p orbitals move to a lower energy area with the increase of B contents, which leads to the increase of shear and Young’s moduli of M _x B _y . Furthermore, for M₃B₂ borides, the Cr-B bonds and Cr–Cr bonds are much stronger than the W-B & Mo-B bonds, and W-W & Mo-Mo bonds, respectively, which leads to Cr _x B _y yielding the largest values of elastic moduli.     

非负载镍催化剂的2-乙基蒽醌加氢活性及其氢吸脱附性质

 分别制备了金属镍粉、兰尼镍、Ni-B非晶态合金及镧掺杂的Ni-B非晶态合金(Ni-B-La)催化剂,研究了催化剂的氢吸附和脱附性质以及对2-乙基蒽醌加氢反应的催化性能. 结果表明,金属镍粉、兰尼镍和Ni-B催化剂表面均具有两种氢吸附位: 弱吸附位和强吸附位. Ni-B-La催化剂表面只有氢的强吸附位,其强吸附氢量与兰尼镍相当. 推测只有氢的强吸附位是2-乙基蒽醌加氢反应的活性中心,并且Ni-B-La催化剂上的强吸附氢较兰尼镍上的更活泼,因而Ni-B-La非晶态合金催化剂对加氢反应的催化活性高于兰尼镍.     

Analytical Electron Microscopy Examination of the γ′/γ Interfaces in a Ni-Based Superalloy

The investigation of microstructure and chemical composition of the and phases were performed in a Ni-base superalloy by means of analytical electron microscopy. The distribution of particular elements in the alloy was revealed using X-ray mapping in a transmission electron microscope. The detected concentration profiles of alloying elements at the / interface were relatively sharp in the case of cuboidal shape of the phase while they resembled the classical diffusion profile for the oval phase. The quantitative analysis of the phase revealed much higher content of Al and lower of Ti, W, Co and Mo in the oval precipitates compared to cuboidal ones. This result is attributed to the different solidification paths, which is eutectic for the cuboidal precipitates and peritectic for the oval precipitates.     

Evolution of helium bubbles in nickel-based alloy by post-implantation annealing

Nickel-based alloys have been considered as candidate structural materials used in generation IV nuclear reactors serving at high temperatures. In the present study, alloy 617 was irradiated with 180-keV helium ions to a fluence of 3.6×10¹⁷ ions/cm² at room temperature. Throughout the cross-section transmission electron microscopy (TEM) image, numerous over-pressurized helium bubbles in spherical shape are observed with the actual concentration profile a little deeper than the SRIM predicted result. Post-implantation annealing was conducted at 700 ℃ for 2 h to investigate the bubble evolution. The long-range migration of helium bubbles occurred during the annealing process, which makes the bubbles of the peak region transform into a faceted shape as well. Then the coarsening mechanism of helium bubbles at different depths is discussed and related to the migration and coalescence (MC) mechanism. With the diffusion of nickel atoms slowed down by the alloy elements, the migration and coalescence of bubbles are suppressed in alloy 617, leading to a better helium irradiation resistance.     

Characterization and oxidation behavior of NiCoCrAlY coating fabricated by electrophoretic deposition and vacuum heat treatment

Electrophoretic deposition (EPD) was showed to be a feasible and convenient method to fabricate NiCoCrAlY coatings on nickel based supperalloys. The microstructure and composition of the NiCoCrAlY coatings after vacuum heat treatment were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX). Isothermal-oxidation test was performed at 1100 °C in static air for 100 h. The results show that the major phases in electrophoretic deposited and vacuum heat treated NiCoCrAlY coating are γ-Ni and γ′-Ni₃Al phases, also there is an extremely small quantity of Al₂O₃ in the coating. Composition fluctuations occur in the coating and a certain amount of titanium diffuse from the superalloy substrate to the top of the coating during vacuum heat treatment. The oxidation test results exhibit that the oxidation kinetics of this coating has two typical stages. The protective oxide layer is mainly formed in the initial linear growth stage and then the oxide layer hinders further oxidation of the coating in the subsequent parabolic growth stage. The coating can effectively protect the superalloy substrate from oxidation. A certain amount of rutile TiO₂ is formed in the coating during oxidation and it is adverse to the oxidation resistance of the coating.     

Investigations on the growing, cracking and spalling of oxides scales of powder metallurgy Rene95 nickel-based superalloy

The surface and cross-sectional morphologies of powder metallurgy (PM) Rene95 nickel-based superalloy after 100 h oxidation in the temperature range of 700-1100 °C were investigated. It is shown that oxides nucleate first on the surface of the alloy and form an oxides scale. Afterwards, oxides scale endures decohesion, rumpling, cracking and finally spalling owing to the weak cohesive strength of the scale/alloy interface. The XRD and EDS analyses confirmed that the oxides scale of PM Rene95 superalloy is mainly composed by Cr₂O₃ at 800 °C and NiCr₂O₄ is the main spinel at 1100 °C. The subsequent analysis of internal stress verified that cracking and spalling are caused by growth stress and promoted by thermal stress. On these bases, improvement of the cohesive strength of the scale/alloy interface is considered to be the main way to increase the oxidation resistance of PM Rene95 superalloy.