Hydroxide Nanoclusters Research Articles

Oxygen vacancy-rich amorphous FeNi hydroxide nanoclusters as an efficient electrocatalyst for water oxidation

In this work, a one-pot strategy is presented to directly synthesize amorphous FexNiy hydroxide nanoclusters (denoted as ANC-FexNiy, <2 nm) with oxygen vacancies induced by ionic liquids. The ANC-FexNiy catalyst presents abundant catalytic sites and high intrinsic conductivity. As such, the optimized ANC-Fe1Ni2 exhibits high activity in oxygen evolution reaction (OER) with a Tafel slope of 39 mV dec–1 and an overpotential of 266 mV at 10 mA cm−2. Notably, the optimized ANC-Fe1Ni2 shows an extraordinarily large mass activity of 3028 A gFeNi–1 at the overpotential of 300 mV, which is ∼24-fold of commercial RuO2 catalyst. The superior activity of these FexNiy hydroxide nanoclusters is ascribed to (i) the amorphous and distorted structure with abundant oxygen vacancies, and (ii) enhanced active site density by downsizing the ANC-FexNiy clusters. This strategy provides a novel route for enhancing OER electrocatalytic performance and highly encouraging for the future application of amorphous metal hydroxides in catalysis.

Rapid Gelling of Guar Gum Hydrogel Stabilized by Copper Hydroxide Nanoclusters for Efficient Removal of Heavy Metal and Supercapacitors.

In this paper, guar gum (GG) hydrogel has been successfully prepared by adding GG and Cu2+ mixture into an alkaline medium. The formation mechanism of the hydrogel has been investigated through various techniques. Results reveal GG facilitates the formation of ultrafine copper hydroxide clusters with a diameter of ∼3 nm. Moreover, these nanoclusters bring about a rapid gelling of GG within 10 ms. The synthesized hydrogel is applied to the adsorption of heavy metal ions from wastewater. The hydrogel shows excellent removal efficiency in removing various heavy metal ions. Besides, the hydrogel derived porous carbon exhibits high specific capacitance (281 F/g at 1 A/g) and excellent rate capacity. The high contaminant removal efficiency character and excellent electrochemical performance endow GG hydrogel with potential applications in the environmental and energy storage field.

Electrochromic Thin Films Based on NiAl Layered Double Hydroxide Nanoclusters for Smart Windows and Low-Power Displays

To develop electrochromic thin films for smart windows and low-power displays, homogeneous thin films were produced by spin coating colloidal NiAl layered double hydroxide (LDH) nanocluster solutions on a fluorine-doped tin oxide (FTO) glass substrate. The nano-LDH dispersion was synthesized via a facile one-step epoxide mediated process at room temperature. In situ relative transmittance measurements at 400 nm, recorded during potential scans in cyclic voltammetry or differential pulse chronoamperometry, showed the electrochromic behavior of the homogeneous thin films. The impact of various parameters on the electrochromic properties of the films was detailed, such as the thickness of the film, the nature of the electrolyte, and the presence of electroactive anions. The electrochromic properties, namely, the change in transmittance (ΔT) and the bleaching reversibility, were greatly improved using alkaline metal hydroxide as the electrolyte and in the presence of Fe(CN)64–. The performances that we reached from the deposition of nanoclusters can be advantageously compared to the literature with ΔT = 70% and fast and good reversibility. Upon calcination, the NiAl-LDH film converted into mixed oxides (NiO and NiAl2O4). The higher the calcination temperature, the lower was the ΔT value. The presence of porosity within the thin films, through the introduction of sacrificial polymeric beads and then decomposition at 400 °C, was investigated, highlighting an enhancement of the ΔT value attributed to better accessibility to the nickel redox sites.

Interstratified heterostructures of metal hydroxide nanoclusters and MoS2 monolayers with improved electrode performance.

Interstratified 2D nanohybrids of chromium hydroxide-molybdenum disulfide with improved electrode functionality are synthesized by the self-assembly of anionic monolayered MoS2 nanosheets with cationic chromium hydroxide nanoclusters. The intercalative hybridization of MoS2 with chromium hydroxide nanoclusters leads to a significant increase of basal spacing as well as to the formation of an open porous stacking structure. This is the first example of metal hydroxide nanocluster-pillared transition metal dichalcogenide (TMD) hybrid materials. According to extended X-ray absorption fine structure analysis, open tetrameric chromium hydroxide nanoclusters are stabilized in-between metallic 1T'-MoS2 monolayers. In comparison with the pristine MoS2 material, the chromium hydroxide-pillared molybdenum disulfide nanohybrids show remarkably improved charge storage capacity with excellent rate performance for lithium ion batteries, highlighting the beneficial effect of pillaring with metal hydroxides on the electrode performance of MoS2. The improvement of electrode functionality upon hybridization is attributable to the increase of basal spacing, the stabilization of metallic 1T'-MoS2 content, the improvement of charge transfer kinetics, and the stabilization of the open porous structure upon electrochemical cycling. The present study clearly demonstrates that an electrostatically-driven self-assembly between exfoliated TMD nanosheets and cationic inorganic nanoclusters can provide an effective way of synthesizing heterostructured hybrid electrode materials with improved performance.

Microparticles with hetero-nanointerfaces: controlled assembly of cobalt hydroxide and nickel hydroxide nanoclusters towards improved electrochemical functions

Hybridization of electrochemical functions derived from large hetero-interfaces by assembly of layered metal hydroxide nanoclusters.

Synthesis of Co–Al layered double hydroxide nanoclusters as reduction nanocatalyst in aqueous media

Layered double hydroxides (LDHs) have attracted attention as green materials due to their catalytic ability in benign aqueous solvents. We here demonstrate the synthesis of colloidal Co–Al LDH nanoclusters with an average size of <10 nm via a facile liquid-phase reaction for the enhancement of the catalytic activity. To the best of our knowledge, the present LDH is the smallest Co–Al LDH with an extremely large surface area and stability in an aqueous solvent, forming a stable and concentrated colloidal solution as high as 40 g/L. We investigated the formation mechanism, and the catalytic activity of Co–Al LDH nanoclusters. The Co–Al LDH nanoclusters showed 47 times higher rate of the reduction of dye molecules in the aqueous media than standard Co–Al LDH particles with a micrometer size. LDH nanoclusters demonstrated here are promising green nanocatalysts for the aqueous reaction processes.

Modification of Wide‐Band‐Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible‐Light Water Oxidation

AbstractCobalt‐based compounds, such as cobalt(II) hydroxide, are known to be good catalysts for water oxidation. Herein, we report that such cobalt species can also activate wide‐band‐gap semiconductors towards visible‐light water oxidation. Rutile TiO2 powder, a well‐known wide‐band‐gap semiconductor, was capable of harvesting visible light with wavelengths of up to 850 nm, and thus catalyzed water oxidation to produce molecular oxygen, when decorated with cobalt(II) hydroxide nanoclusters. To the best of our knowledge, this system constitutes the first example that a particulate photocatalytic material that is capable of water oxidation upon excitation by visible light can also operate at such long wavelengths, even when it is based on earth‐abundant elements only.

Modification of Wide-Band-Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible-Light Water Oxidation.

Cobalt-based compounds, such as cobalt(II) hydroxide, are known to be good catalysts for water oxidation. Herein, we report that such cobalt species can also activate wide-band-gap semiconductors towards visible-light water oxidation. Rutile TiO2 powder, a well-known wide-band-gap semiconductor, was capable of harvesting visible light with wavelengths of up to 850 nm, and thus catalyzed water oxidation to produce molecular oxygen, when decorated with cobalt(II) hydroxide nanoclusters. To the best of our knowledge, this system constitutes the first example that a particulate photocatalytic material that is capable of water oxidation upon excitation by visible light can also operate at such long wavelengths, even when it is based on earth-abundant elements only.

Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

On the mechanism of oxygen reduction on single-crystal and polycrystalline Pt electrodes in alkaline media

The characteristics of oxygen reduction on various platinum electrodes (smooth polycrystalline metal, Pt(hkl) single-crystals, disperse materials) in alkaline media are interpreted. The interpretation was based on the theory of electrochemical processes with a slow subsequent heterogeneous reaction. The dependence of polarization curve slopes in Tafel coordinates on the type of electrode material surface is explained based on the Temkin approach as the energetic inhomogeneity of the electrode surface. The energetic inhomogeneity is associated with the appearance of surface hydroxide nanoclusters of various composition based on oxidized platinum atoms which simultaneously represent the surface lattice defects s, dPt. The multistage heterogeneous chemical reaction is interpreted as the innercluster oxidation of the previously electrochemically reduced s, dPt atoms by oxygen molecules.

Hydrothermal synthesis of inorganic–organic hybrid gadolinium hydroxide nanoclusters with controlled size and morphology

A series of gadolinium hydroxide [Gd(OH)3] nanoclusters having different morphologies was synthesized in the presence of 3,4-dihydroxy hydrocinnamic acid (DHCA), an organic modifier, under subcritical water conditions. These well-shaped Gd(OH)3 clusters are composed of many nanorods in a parallel orientation, rather than a disordered aggregation of nanorods, which are linked together by organic DHCA molecules. Here DHCA works as an inter-linker to form these cluster-like structures through coordination bonds. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and SQUID magnetometry. We investigated the effect of the concentrations of DHCA and KOH on the size and morphology of the Gd(OH)3 clusters. Their possible formation mechanism is also briefly discussed.

Mesoporous Iron Oxide-Layered Titanate Nanohybrids: Soft-Chemical Synthesis, Characterization, and Photocatalyst Application

Mesoporous iron oxide-layered titanate nanohybrids have been synthesized through a reassembling reaction between exfoliated titanate nanosheets and iron hydroxide nanoclusters, in which an electrostatic attraction between both nanosized species could be achieved at low pH of 1.5. The formation of the layer-by-layer ordered heterostructure with the repeating unit of 1.33 nm was clearly evidenced by powder X-ray diffraction and transmission electron microscopic analysis. According to Fe K-edge X-ray absorption spectroscopy, the hybridized iron oxide crystallizes with loosely packed network of three edge-shared FeO6 octahedra units. N2 adsorption−desorption isotherm and diffuse reflectance UV−vis measurements clearly demonstrated that the present iron oxide-layered titanate nanohybrids showed greatly expanded surface areas with mesopores (∼190−230 m2g−1) and narrow bandgap energies (∼2.3 eV), which are of crucial importance in creating a visible light-active photocatalyst. The test of photocatalytic activity...

Formation of Colloidal Copper Hydroxides and Oxides Biopolymeric Interfaces

ABSTRACTLight sensitive colloidal particles of copper hydrous oxides were prepared at interfaces of exopolymeric materials. Dislike copper oxide or hydroxide nanoclusters were obtained which might be useful as p-type semiconductors. The colloidal Cu2O xH2O and Cu(OH)2 particles reveal fractal dimensions of D = 2.15 ±0.05 for Cu(OH)2 and D= 1.75 ±0.07 for Cu2O xH20.