Showing papers on "Nickel published in 2014"

Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis

Abstract: There is ongoing research into new electrocatalysts for hydrogen production from water splitting. Here, the authors report the electrocatalytic performance of nickel/nickel oxide heterostructures on carbon nanotubes, and are able to assemble a water electrolyzer operated by a single-cell 1.5 V battery.

Nickel–Cobalt Layered Double Hydroxide Nanosheets for High-performance Supercapacitor Electrode Materials

Abstract: A facile and novel one-step method of growing nickel-cobalt layered double hydroxide (Ni-Co LDH) hybrid films with ultrathin nanosheets and porous nanostructures on nickel foam is presented using cetyltrimethylammonium bromide as nanostructure growth assisting agent but without any adscititious alkali sources and oxidants. As pseudocapacitors, the as-obtained Ni-Co LDH hybrid film-based electrodes display a significantly enhanced specific capacitance (2682 F g−1 at 3 A g−1, based on active materials) and energy density (77.3 Wh kg−1 at 623 W kg−1), compared to most previously reported electrodes based on nickel-cobalt oxides/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni-Co LDH hybrid film as the positive electrode material and porous freeze-dried reduced graphene oxide (RGO) as the negative electrode material, exhibits an ultrahigh energy density (188 Wh kg−1) at an average power density of 1499 W kg−1 based on the mass of active material, which greatly exceeds the energy densities of most previously reported nickel or cobalt oxide/hydroxide-based asymmetric supercapacitors.

Graphene–nickel interfaces: a review

Abstract: Graphene on nickel is a prototypical example of an interface between graphene and a strongly interacting metal, as well as a special case of a lattice matched system. The chemical interaction between graphene and nickel is due to hybridization of the metal d-electrons with the π-orbitals of graphene. This interaction causes a smaller separation between the nickel surface and graphene (0.21 nm) than the typical van der Waals gap-distance between graphitic layers (0.33 nm). Furthermore, the physical properties of graphene are significantly altered. Main differences are the opening of a band gap in the electronic structure and a shifting of the π-band by ∼2 eV below the Fermi-level. Experimental evidence suggests that the ferromagnetic nickel induces a magnetic moment in the carbon. Substrate induced geometric and electronic changes alter the phonon dispersion. As a consequence, monolayer graphene on nickel does not exhibit a Raman spectrum. In addition to reviewing these fundamental physical properties of graphene on Ni(111), we also discuss the formation and thermal stability of graphene and a surface-confined nickel-carbide. The fundamental growth mechanisms of graphene by chemical vapor deposition are also described. Different growth modes depending on the sample temperature have been identified in ultra high vacuum surface science studies. Finally, we give a brief summary for the synthesis of more complex graphene and graphitic structures using nickel as catalyst and point out some potential applications for graphene–nickel interfaces.

Redox Control and High Conductivity of Nickel Bis(dithiolene) Complex π‑Nanosheet: A Potential Organic Two-Dimensional Topological Insulator

Abstract: A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is −3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or −1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 × 102 S cm–1, which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842).

Nickel phosphide: the effect of phosphorus content on hydrogen evolution activity and corrosion resistance in acidic medium

Abstract: Transition metal phosphides possess novel, structural, physical and chemical properties and are an emerging new class of materials for various catalytic applications. Electroplated or electrolessly plated nickel phosphide alloy materials with achievable phosphorus contents <15 at% P are known to be more corrosion resistant than nickel alone, and have been investigated as hydrogen evolution catalysts in alkaline environments. However, there is significant interest in developing new inexpensive catalysts for solid polymer electrolyte electrolysers which require acid stable catalysts. In this paper, we show that by increasing the phosphorus content beyond the limit available using electroplating techniques (∼12 at% P), the nickel based phosphides Ni12P5 and Ni2P with higher levels of phosphorus (29 and 33 at% P) may be utilised for the hydrogen evolution reaction (HER) in acidic medium. Corrosion resistance in acid is directly correlated with phosphorus content – those materials with higher phosphorus content are more corrosion resistant. Hydrogen evolution activity in acid is also correlated with phosphorus content – Ni2P based catalysts appear to be more active for the hydrogen evolution reaction than Ni12P5. Electrochemical kinetic studies of the HER reveal high exchange current densities and little deviation in the Tafel slope especially in the lower overpotential regime for these nickel phosphide catalysts. The electrochemical impedance spectroscopy response of the respective system in acidic medium reveals the presence of two time constants associated with the HER.

Ultrasmall Dispersible Crystalline Nickel Oxide Nanoparticles as High‐Performance Catalysts for Electrochemical Water Splitting

Abstract: Ultrasmall, crystalline, and dispersible NiO nanoparticles are prepared for the first time, and it is shown that they are promising candidates as catalysts for electrochemical water oxidation. Using a solvothermal reaction in tert-butanol, very small nickel oxide nanocrystals can be made with sizes tunable from 2.5 to 5 nm and a narrow particle size distribution. The crystals are perfectly dispersible in ethanol even after drying, giving stable transparent colloidal dispersions. The structure of the nanocrystals corresponds to phase-pure stoichiometric nickel(ii) oxide with a partially oxidized surface exhibiting Ni(iii) states. The 3.3 nm nanoparticles demonstrate a remarkably high turn-over frequency of 0.29 s–1 at an overpotential of g = 300 mV for electrochemical water oxidation, outperforming even expensive rare earth iridium oxide catalysts. The unique features of these NiO nanocrystals provide great potential for the preparation of novel composite materials with applications in the field of (photo)electrochemical water splitting. The dispersed colloidal solutions may also find other applications, such as the preparation of uniform hole-conducting layers for organic solar cells.

Scalable self-growth of Ni@NiO core-shell electrode with ultrahigh capacitance and super-long cyclic stability for supercapacitors

Abstract: Three-dimensional (3D) electrodes have been demonstrated to be promising candidates for high-performance supercapacitors because of their unique architectures and outstanding electrochemical properties. However, the fabrication process for current 3D electrodes is not scalable. Herein, a novel and cost-effective activation process has been developed to macroscopically produce 3D porous Ni@NiO core-shell electrodes with enhanced electrochemical properties. The porous Ni@NiO core-shell electrode obtained by activated commercial Ni foam (NF) in a 3 M HCl solution yields an ultrahigh areal capacitance of 2.0 F cm−2 at a high current density of 8 mA cm−2, which is substantially higher than that of most reported 3D NF-based electrodes. Moreover, the activated NF (ANF) electrode exhibited super-long cycling stability. Owing to the increased accessible surface area and continual formation of electrochemically active NiO during cycling, the areal capacitance of the ANF electrode did not exhibit any decay and instead increased from 0.47 to 1.27 F cm−2 after 100 000 cycles at 100 mV s−1. This is the best cycling stability achieved by a 3D NF-based electrode. Additionally, a high-performance asymmetrical supercapacitor (ASC) device based on the as-prepared ANF cathode and a reduced graphene oxide (RGO) anode was also prepared. The ANF//RGO-ASC device was able to deliver a maximum energy density of 1.06 mWh cm−3 and a maximum power density of 0.42 W cm−3. Researchers from China have discovered a cost-effective way to produce supercapacitors on large scales using nickel foam. This three-dimensional porous metal is an ideal electrode for high-capacity energy storage because of its lightweight, corrosion-resistant structure. To achieve supercapacitance, however, researchers must insert active substances, such as graphene, deep into the nickel pores. Xihong Lu and colleagues from Sun Yat-Sen University solved this problem by immersing commercial-grade nickel foam into hot hydrochloric acid for several minutes. The one-step reaction pitted the formerly smooth nickel foam surface and created a thin outer ‘shell’ of nickel oxide that surrounded an inner nickel ‘core’. Electrochemical experiments revealed that the favorable core–shell structure, combined with a more accessible surface area achieved from the acid etching, yielded an energy-dense supercapacitor electrode that was effective for more than 100,000 charge–recharge cycles. A novel and cost-effective activation process has been developed to macroscopically produce three-dimensional (3D) porous Ni@NiO core-shell electrode by activated Ni foam (ANF) in HCl aqueous solution. The ANF electrode yielded a remarkable areal capacitance of 2.0 F cm−2 at a high current density of 8 mA cm−2 and exhibited ultrahigh long-term cycling stability without any decay of capacitance after 100 000 cycles.

Homogeneous electrocatalytic water oxidation at neutral pH by a robust macrocyclic nickel(II) complex.

Abstract: The development of an earth-abundant, first-row water oxidation catalyst that operates at neutral pH and low overpotential remains a fundamental chemical challenge. Herein, we report the first nickel-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at neutral pH and low overpotential in phosphate buffer. The results of DFT calculations verify that the OO bond formation in catalytic water oxidation prefers a HOOH coupling mechanism from a cis-isomer of the catalyst.

Porous Nickel Hydroxide–Manganese Dioxide-Reduced Graphene Oxide Ternary Hybrid Spheres as Excellent Supercapacitor Electrode Materials

Abstract: This paper reports the first nickel hydroxide–manganese dioxide–reduced graphene oxide (Ni(OH)2-MnO2-RGO) ternary hybrid sphere powders as supercapacitor electrode materials. Due to the abundant porous nanostructure, relatively high specific surface area, well-defined spherical morphology, and the synergetic effect of Ni(OH)2, MnO2, and RGO, the electrodes with the as-obtained Ni(OH)2-MnO2-RGO ternary hybrid spheres as active materials exhibited significantly enhanced specific capacitance (1985 F·g–1) and energy density (54.0 Wh·kg–1), based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-RGO hybrid spheres-based asymmetric supercapacitor also showed satisfying energy density and electrochemical cycling stability.

Improvement of the Seebeck coefficient of PEDOT:PSS by chemical reduction combined with a novel method for its transfer using free-standing thin films

Abstract: A simple method for improving the Seebeck coefficient of PEDOT:PSS up to 161 μV K−1 is presented and combined with a new process for transferring thick (>10 μm) films of PEDOT:PSS onto substrates with various shapes, and in particular onto flexible substrates. These reduced transferred films have been used in combination with a nickel ethylenetetrathiolate coordination polymer to fabricate cheap and flexible heat flux sensors.

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes

Abstract: This study deals with the exploration of NixCo1−xFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4–6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co0.4Ni0.6Fe2O4 (154.02 m2 g−1). Co0.4Ni0.6Fe2O4 showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe2O4 was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH4 on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni2+ in to the cobalt ferrite lattice due to octahedral site preference of Ni2+. Almost 99% degradation was achieved in 20 min using NiFe2O4 nanoparticles as catalyst.

Reversible CO Binding Enables Tunable CO/H2 and CO/N2 Separations in Metal–Organic Frameworks with Exposed Divalent Metal Cations

Abstract: Six metal–organic frameworks of the M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) structure type are demonstrated to bind carbon monoxide reversibly and at high capacity. Infrared spectra indicate that, upon coordination of CO to the divalent metal cations lining the pores within these frameworks, the C–O stretching frequency is blue-shifted, consistent with nonclassical metal-CO interactions. Structure determinations reveal M–CO distances ranging from 2.09(2) A for M = Ni to 2.49(1) A for M = Zn and M–C–O angles ranging from 161.2(7)° for M = Mg to 176.9(6)° for M = Fe. Electronic structure calculations employing density functional theory (DFT) resulted in good agreement with the trends apparent in the infrared spectra and crystal structures. These results represent the first crystallographically characterized magnesium and zinc carbonyl compounds and the first high-spin manganese(II), iron(II), cobalt(II), and nickel(II) carbonyl species. Adsorption isotherms ind...

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Abstract: Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible-light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground-state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.

Nickel Oxide Hole Injection/Transport Layers for Efficient Solution-Processed Organic Light-Emitting Diodes

Abstract: Solution-processed nickel oxides (s-NiOx) are used as hole injection and transport layers in solution-processed organic light-emitting diodes (OLEDs). By increasing the annealing temperature, the nickel acetate precursor fully decomposes and the s-NiOx film shows larger crystalline grain sizes, which lead to better hole injection and transport properties. UV–ozone treatment on the s-NiOx surface is carried out to further modify its surface chemistry, improving the hole injection efficiency. The introduction of more dipolar species of nickel oxy-hydroxide (NiO(OH)) is evidenced after the treatment. Dark injection–space charge limited (DI–SCL) transient measurement was carried out to compare the hole injection efficiency of s-NiOx and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole injection layers (HIL). The UV–ozone treated s-NiOx shows significantly better hole injection, with a high injection efficiency of 0.8. With a p-type thin film transistor (TFT) configuration, the high-tem...

Enhanced oxygen evolution activity by NiOx and Ni(OH)2 nanoparticles

Abstract: Small nanoparticles of nickel oxide and nickel hydroxide were investigated for the oxygen evolution reaction (OER) in alkaline solutions. These nanoparticles showed excellent catalytic activity, giving a current density of 10 mA cm−2 at overpotentials (η) of 300 and 330 mV for Ni(OH)2 and NiOx, respectively. The catalytic activity was comparable to that of the best mixed metal oxide catalysts under the same conditions. The activity was significantly higher than that of electrochemically formed Ni(OH)2 and NiOx films, demonstrating the benefit of nanostructuring. Pretreatment of the working electrode was important for the activity and stability of the catalyst layer on the electrode.

ZnCo2O4 nanowire arrays grown on nickel foam for high-performance pseudocapacitors

Abstract: Uniform ZnCo2O4 nanowire arrays were directly grown on nickel foam through a facile hydrothermal method and subsequent thermal treatment process. The ZnCo2O4 nanowires have diameters of about 100 nm and lengths of up to 5 μm. The as-obtained ZnCo2O4 nanowire array loaded nickel foam can be directly applied as an electrode for high-performance supercapacitors. Electrochemical measurements show that the ZnCo2O4/nickel foam electrode has high specific capacitance (1625 F g−1 at 5 A g−1), excellent rate capability (59% capacitance retention at 80 A g−1) and good cycling stability (94% capacitance retention over 5000 charge–discharge cycles). This work demonstrates that ZnCo2O4 nanowires are highly desirable for application as advanced electrochemical electrode materials.