Zeolitic-imidazolate frameworks-derived Co3S4/NiS@Ni foam heterostructure as highly efficient electrocatalyst for oxygen evolution reaction

Transition metals sulfide-based nanomaterials have recently received significant attention as a promising cathode electrode for the oxygen evolution reaction (OER) due to their easily tunable electronic, chemical, and physical properties. However, the poor electrical conductivity of metal-sulfide materials impedes their practical application in energy devices. Herein, firstly nano-sized crystals of cobalt-based zeolitic-imidazolate framework (Co-ZIF) arrays were fabricated on nickel-form (NF) as the sacrificial template by a facile solution method to enhance the electrical conductivity of the electrocatalyst. Then, the Co₃S₄/NiS@NF heterostructured arrays were synthesized by a simple hydrothermal route. The Co-ZIFs derived Co₃S₄ nanosheets are grown successfully on NiS nanorods during the hydrothermal sulfurization process. The bimetallic sulfide-based Co₃S₄/NiS@NF-12 electrocatalyst demonstrated a very low overpotential of 119 mV at 10 mA cm^?2 for OER, which is much lower than that of mono-metal sulfide NiS@NF (201 mV) and ruthenium-oxide (RuO₂) on NF (440 mV) electrocatalysts. Furthermore, the Co₃S₄/NiS@NF-12 electrocatalyst showed high stability during cyclic voltammetry and chronoamperometry measurements. This research work offers an effective strategy for fabricating high-performance non-precious OER electrocatalysts.     

Plasma-assisted CO2 reforming of methane over Ni-based catalysts: Promoting role of Ag and Sn secondary metals

Carbon dioxide (CO₂) and methane (CH₄) are the primary greenhouse gases (GHGs) that drive global climate change. CO₂ reforming of CH₄ or dry reforming of CH₄ (DRM) is used for the simultaneous conversion of CO₂ and CH₄ into syngas and higher hydrocarbons. In this study, DRM was investigated using Ag–Ni/Al₂O₃ packing and Sn–Ni/Al₂O₃ packing in a parallel plate dielectric barrier discharge (DBD) reactor. The performance of the DBD reactor was significantly enhanced when applying Ag–Ni/Al₂O₃ and Sn–Ni/Al₂O₃ due to the relatively high electrical conductivity of Ag and Sn as well as their anti-coke performances. Using Ag–Ni/Al₂O₃ consisting of 1.5 wt% Ag and 5 wt% Ni/Al₂O₃ as the catalyst in the DBD reactor, 19% CH₄ conversion, 21% CO₂ conversion, 60% H₂ selectivity, 81% CO selectivity, energy efficiency of 7.9% and 0.74% (by mole) coke formation were achieved. In addition, using Sn–Ni/Al₂O₃, consisting of 0.5 wt% Sn and 5 wt% Ni/Al₂O₃, 15% CH₄ conversion, 19% CO₂ conversion, 64% H₂ selectivity, 70% CO selectivity, energy efficiency of 6.0%, and 2.1% (by mole) coke formation were achieved. Sn enhanced the reactant conversions and energy efficiency, and resulted in a reduction in coke formation; these results are comparable to that achieved when using the noble metal Ag. The decrease in the formation of coke could be correlated to the increase in the CO selectivity of the catalyst. Good dispersion of the secondary metals on Ni was found to be an important factor for the observed increases in the catalyst surface area and catalytic activities. Furthermore, the stability of the catalytic reactions was investigated for 1800 min over the 0.5 wt% Ag-5 wt% Ni/Al₂O₃ and 0.5 wt% Sn-5 wt% Ni/Al₂O₃ catalysts. The results showed an increase in the reactant conversions with an increase in the reaction time.     

Theoretical study the component and facet dependence of HER performance on nickel phosphides surfaces

Energy depletion and environmental pollution are still serious challenges for human beings. The application of hydrogen energy should be a promising strategy to address this issue. However, the hydrogen production should be one shortcoming for hydrogen energy. The hydrogen evolution reaction (HER) based on electrocatalysis is an effective way to enhance the hydrogen generation with small energy consumption under ambient conditions. Many works have been devoted to develop high performance catalysts to satisfy the HER processes. Nevertheless, the mechanism about facet-dependence and composition-dependence influence is still need to deeply study. Hereon, based on density functional theory calculations, the [100], [110], and [111] facets of Ni_xP_y (Ni₃P, Ni₂P, NiP, NiP₂, NiP₃) systems were created and their HER catalytic activity were used to reveal the underline mechanism. By analyzing the variation of Gibbs free energy, it was found that the structural composition has a greater effect on HER than the facet. Significantly, the Ni₂P(111) surface with Ni/P-termination has the best HER performance for all samples in present work. Through exploring the electron transfer of H with surrounding atoms during the HER process, the H adsorption mechanism as well as its reaction mechanism has been revealed. The deep insights in this work provide an important fundamental that the contents of non-metal for compounds catalysts can heavily influence the performance of HER, which should give more guidance for designing new catalysts.     

Pseudocapacitive contributions to electrochemical kinetics in NiOx electrochromic anodes

Because of its ability to change optical absorption dynamically by applied electric field, nickel oxide (NiO) is a promising anodic material in smart windows, which can improve energy conversion efficiency in construction buildings. Although many works have achieved high electrochromic performance with different method. The underlying mechanism is still not fully investigated. In this article, we prepared the NiO films with large specific surface area and high stability by electron beam evaporation. X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to figure out the surface morphology and composition of as-deposited films. Afterwards, the electrochemical properties and optical performance of the prepared NiO films were investigated. On this basis, the origin of surface charge was fully analyzed by cyclic voltammetry and diffusion coefficient test. These experimental and theoretical results firmly confirm that both the surface reaction and capacitive effect bring about the excellent EC performance in NiO films. These results not only provide clear evidence about electrochemical kinetics in NiO films, but also offer some useful guidelines for the design of EC materials with higher performance and longer stability.     

Efficient utilization of silanol group in rice husk to promote the synthesis of Ni-phyllosilicate for CO2 methanation

It is a challenge to prepare Ni-phyllosilicate catalysts deriving from the reaction of nickel salts and biomass-based silica with high Ni contents. In order to efficiently synthesize nickel phyllosilicate, the acid-treated rice husk without calcination (P-R) was directly used as the raw material. The as-synthesized Ni-phyllosilicate (N/P-R) exhibited high nickel content of 46.7 wt% owing to utilization of the abundant silanol group in the fresh rice husk. On the contrary, the Ni content of Ni-phyllosilicate sample (N/R–S) prepared using the calcinated rice husk-based silica was only 4.8 wt% because of the loss of silanol group during calcination process. As a result, N/P-R displayed much higher catalytic activity for CO₂ methanation than N/R–S. It was found that the silanol group was in favour of forming the important intermediate Si(OH)₄, and thereby facilitated the formation of nickel phyllosilicate. In addition, the N/P-R catalyst demonstrated superior stability and excellent anti-sintering ability in the long lifetime test. In short, the proposed method in this work could not only efficiently synthesize nickel phyllosilicate with high Ni content, but also reduce energy consumption and operation steps compared to the one prepared using biomass-based silica.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

Structure and phase-composition of Ti-doped gas atomized Raney-type Ni catalyst precursor alloys

Raney-type Ni precursor alloys containing 75 at.% Al and doped with 0, 0.75, 1.5 and 3.0 at.% Ti have been produced by a gas atomization process. The resulting powders have been classified by size fraction with subsequent investigation by powder XRD, SEM and EDX analysis. The undoped powders contain, as expected, the phases Ni₂Al₃, NiAl₃ and an Al-eutectic. The Ti-doped powders contain an additional phase with the TiAl₃ DO₂₂ crystal structure. However, quantitative analysis of the XRD results indicate a far greater fraction of the TiAl₃ phase is present than could be accounted for by a simple mass balance on Ti. This appears to be a (Ti_xNi_1−x)Al₃ phase in which higher cooling rates favour small x (low Ti-site occupancy by Ti atoms). SEM and EDX analysis reveal that virtually all the available Ti is contained within the TiAl₃ phase, with negligible Ti dissolved in either the Ni₂Al₃ or NiAl₃ phases.     

Study of the effect of noble metal promotion in Ni-based catalyst for the Sabatier reaction

This paper reports the preparation and the evaluation of the performance of Ni-based powder catalysts with low nickel loading on the CO2 methanation reaction, that is an integral part of the power-to-gas (PtG) technology. CeO₂, CeZrO₄ and CeO₂/SiO₂ were selected as possible supports, and the results of this first screening pointed out that 10%Ni/CeO₂ catalyst could offer the best reaction performances because of ceria's peculiar characteristics. Moreover, the promotion of this promising formulation with the addition of a small amount of noble metals (Pt, Ru, Rh) was investigated, showing that platinum in particular can enhance the catalyst performances. A further study related to the noble metal loading pointed out that platinum and ruthenium have a different optimum loading condition: this result, together with the activity tests performed on monometallic formulations with only the noble metal, suggested that the two metals are able to catalyse two different reactions, thus promoting two different reaction mechanisms.     

Producing fully-lamellar microstructure for wrought beta-gamma TiAl alloys without single α-phase field

Fine-grained fully-lamellar (FL) microstructure is desired for TiAl components to serve as compressor/turbine blades and turbocharger turbine wheels. This study deals with the process and phase transformation to produce FL microstructure for Mo stabilized beta-gamma TiAl alloys without single α-phase field. Unlike the α + γ two-phased TiAl or beta-gamma TiAl with single α-phase field, the wrought multi-phase TiAl–4/6Nb–2Mo–B/Y alloys exhibit special annealing process to obtain FL microstructure. Short-term annealing at temperatures slightly above β-transus is recommended to produce the desired FL microstructure. The related mechanism is to guarantee the sufficient diffusion homogenization of β stabilizers during single β-phase annealing, and further avoid α decomposition by α → γ + β when cooling through α + β + γ phase field. The colony boundary β phase contributes to fine-grained nearly FL microstructure, by retarding the coarsening of the α phase grains.     

A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.