Constructing magnetic Fe3O4‐Au@CeO2 hybrid nanofibers for selective catalytic degradation of organic dyes

Au nanoparticles (Au NPs) play a vital role in heterogeneous catalytic reactions. However, pristine Au NPs usually suffer from poor selectivity and difficult recyclability. In this work, Fe₃O₄‐Au@CeO₂ hybrid nanofibers were prepared via a simple one‐pot redox reaction between HAuCl₄ and Ce (NO₃)₃ in the presence of Fe₃O₄ nanofibers. CeO₂ shell was uniformly coated on the surface of Fe₃O₄ nanofibers to form a unique core‐shell structure, while Au NPs were encapsulated inside the CeO₂ shell. The as‐prepared Fe₃O₄‐Au@CeO₂ hybrid nanofibers have been proved to be positively surface charged due to the formation of CeO₂ shell, enabling them to be good candidates for predominant selective catalytic activity towards the degradation of negatively charged organic dyes. In addition, the Fe₃O₄‐Au@CeO₂ hybrid nanofibers showed magnetic properties, offering them excellent recyclable usability. This work presents a facile and effective solution to prepare magnetic noble metal/metal oxide hybrid nanomaterials with unique chemical structure and surface characteristic for promising applications in heterogeneous catalysis.     

Facile Synthesis of Cuprous Oxide/Gold Nanocomposites for Nonenzymatic Amperometric Sensing of Hydrogen Peroxide

In this work, a facile preparation method of cuprous oxide/gold (Cu₂O/Au) nanocomposite was successfully developed. The process consisted of one‐pot co‐reduction of HAuCl₄ and CuSO₄ using ascorbic acid (AA) as a reducing agent at room temperature under magnetic stirring. The structures and compositions of the as‐prepared products were characterized by SEM, EDS, and XRD. Cyclic voltammetry and chronopotentiometry studies revealed that the as‐prepared cubic Cu₂O/Au nanocomposites showed enhanced performance towards the non‐enzymatic catalytic reduction of hydrogen peroxide (H₂O₂) when compared to single‐component Cu₂O nanocubes. The linear range of H₂O₂ determination spanned over 4 orders of magnitude (1 μM∼16.7 mM) and the detection limit was low as 0.45 μM (S/N=3). The enhanced performance of cubic Cu₂O/Au was attributed to: i) the synergistic effect between Cu₂O and Au, ii) the increase in surface area induced by the reduced size of the nanocubes, and iii) the improved electrical conductivity due to the presence of Au in the particles. Overall, the cubic Cu₂O/Au nanocomposites prepared by the proposed method hold great promise for future practical use in H₂O₂ detection.     

Synthesis of hollow and nanoporous gold/platinum alloy nanoparticles and their electrocatalytic activity for formic acid oxidation

In this work, hollow Au/Pt alloy nanoparticles (NPs) with porous surfaces were synthesized in a two-step procedure. In the first step, tri-component Ag/Au/Pt alloy NPs were synthesized through the galvanic replacement reaction between Ag NPs and aqueous solutions containing a mixture of HAuCl₄ and H₂PtCl₄. In the second step, the Ag component was selectively dealloyed with nitric acid (HNO₃), resulting in hollow di-component Au/Pt alloy NPs with a porous surface morphology. The atomic ratio of Au to Pt in the NPs was easily tunable by controlling the molar ratio of the precursor solution (HAuCl₄ and H₂PtCl₆). Hollow, porous Au/Pt alloy NPs showed enhanced catalytic activity toward formic acid electrooxidation compared to the analogous pure Pt NPs. This improved activity can be attributable to the suppression of CO poisoning via the “ensemble” effect.     

A Novel Hydrogen Peroxide Sensor Based on the Direct Electron Transfer of Catalase Immobilized on Nano‐Sized NiO/MWCNTs Composite Film

MWCNTs‐nanoNiO composite was used as a glassy carbon electrode modifier for construction of a novel catalase nanobiosensor for hydrogen peroxide. The immobilized catalase exhibited excellent electrocatalytic activity towards the reduction of H₂O₂. The resulting amperometric biosensor exhibited a linear response over a concentration range of 200 µM to 2.53 mM with a low detection limit of 19.0 µM. Electrochemical impedance measurements revealed that the modified electrode can be used for the sensitive detection of H₂O₂. The charge transfer resistance found to decrease significantly after enzymatic reaction of nanobiosensor with H₂O₂. The resulting impedance was highly sensitive to H₂O₂ over a linear range of 19–170 nM with a detection limit of 2.4 nM.     

A novel polybenzimidazole-modified gold electrode for the analytical determination of hydrogen peroxide

The imine of polybenzimidazole (PBI) is chemically oxidized by hydrogen peroxide (H₂O₂) in the presence of acetic acid (AcOH). Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopies (XPS) showed that when the AcOH concentration remained constant, the degree of oxidation increased with increasing H₂O₂ levels. Moreover, the imine also exhibited electrochemical redox behavior. Based on these properties, a PBI-modified Au (PBI/Au) electrode was developed as an enzyme-free H₂O₂ sensor. At an applied potential of −0.5 V vs. Ag/AgCl, the current response of the PBI/Au electrode was linear with H₂O₂ concentration over a range from 0.075 to 1.5 mM, with a sensitivity of 55.0 μA mM⁻¹ cm⁻². The probe had excellent stability, with <5% variation from its initial response current after storage at 50 °C for 10 days. Potentially interfering species such as ascorbic or uric acid had no effect on sensitivity. Sensitivity improved dramatically when multiwalled carbon nanotubes (MWCNT) were incorporated in the probe. Under optimal conditions, the detection of H₂O₂ using a MWCNT-PBI/Au electrode was linear from 1.56 μM to 2.5 mM, with a sensitivity of 928.6 μA mM⁻¹ cm⁻². Analysis of H₂O₂ concentrations in urine samples using a MWCNT-PBI/Au electrode produced accurate real-time results comparable to those of traditional HPLC methods.     

Simple Electrodeposition of Dendritic Pd Without Supporting Electrolyte and Its Electrocatalytic Activity Toward Oxygen Reduction and H2O2 Sensing

Metallic palladium (Pd) electrocatalysts for oxygen reduction and hydrogen peroxide (H₂O₂) oxidation/reduction are prepared via electroplating on a gold metal substrate from dilute (5 to 50 mM) aqueous K₂PdCl₄ solution. The best Pd catalyst layer possessing dendritic nanostructures is formed on the Au substrate surface from 50 mM Pd precursor solution (denoted as Pd‐50) without any additional salt, acid or Pd templating chemical species. The Pd‐50 consisted of nanostructured dendrites of polycrystalline Pd metal and micropores within the dendrites which provide high catalyst surface area and further facilitate reactant mass transport to the catalyst surface. The electrocatalytic activity of Pd‐50 proved to be better than that of a commercial Pt (Pt/C) in terms of lower overpotential for the onset and half‐wave potentials and a greater number of electrons (n) transferred. Furthermore, amperometric i–t curves of Pd‐50 for H₂O₂ electrochemical reaction show high sensitivities (822.2 and ?851.9 µA mM^?1 cm^?2) and low detection limits (1.1 and 7.91 µM) based on H₂O₂ oxidation H₂O₂ reduction, respectively, along with a fast response (<1 s).     

Preparation of Gold Microcrystal-Doped TiO2, ZrO2 and Al2O3 Films Through Sol-Gel Process

Au-microcrystal-doped TiO₂, ZrO₂ and Al₂O₃ films were made by sol-gel dip-coating method using titanium, zirconium and aluminum alkoxides with HAuCl₄ · 4H₂O. The influence of the oxide matrix composition on the maximum amount of the Au microcrystals that can be incorporated in the oxide film was examined. Some amount of Au microcrystals were exhausted to the surface of Au microcrystal-doped oxide films when an excess amount of HAuCl₄ · 4H₂O was dissolved in the coating solution. The maximum amount of Au that can be incorporated in the oxide film was found to increase with the increase of the pH point at zero charge (PZC) of the matrix oxide. This should be due to the fact that AuCl ₄ ^- ions are charged negative and also Au microcrystals tend to charge negative, so that the oxide gel with high PZC, which has a tendency to charge positive, may fix the ions and/or microcrystals to its interior. A maximum amount of Au microcrystals as high as 12.6 vol% was attained in an Au:Al₂O₃ film.     

Electron‐Transfer Mediator Microbiosensor Fabrication Based on Immobilizing HRP‐Labeled Au Colloids on Gold Electrode Surface by 11‐Mercaptoundecanoic Acid Monolayer

In this paper, a new strategy for constructing a mediator‐type amperometric hydrogen peroxide (H₂O₂) microbiosensor was described. An electropolymerized thionine film (PTH) was deposited directly onto a gold electrode surface. The resulting redox film was extremely thin, adhered well onto a substrate (electrode), and had a highly cross‐linked network structure. Consequently, horseradish peroxidase (HRP) was successfully immobilized on nanometer‐sized Au colloids, which were supported by thiol‐tailed groups of 11‐mercaptoundecanoic acid (11‐MUA) monolayer covalently bound onto PTH film. With the aid of the PTH mediator, HRP‐labeled Au colloids microbiosensor displayed excellent electrocatalytical response to the reduction of H₂O₂. This matrix showed a biocompatible microenvironment for retaining the native activity of the covalent HRP and a very low mass transport barrier to the substrate, which provided a fast amperometric response to H₂O₂. The proposed H₂O₂ microbiosensor exhibited linear range of 3.5 μM–0.7 mM with a detection limit of 0.05 μM (S/N=3). The response showed a Michaelis‐Menten behavior at larger H₂O₂ concentrations. The K_M^app value for the biosensors based on 24 nm Au colloids was found to be 47 μM, which demonstrated that HRP immobilized on Au colloids exhibited a high affinity to H₂O₂ with no loss of enzymatic activity. This microbiosensor possessed good analytical performance and storage stability.     

Metal Oxide Thin Films Containing Au Nano-Particles Prepared with Gas Diffusion Method

Au particles dispersed thin metal oxide films were prepared from precursor films containing HAuCl₄ with H₂S gas diffusion method. HAuCl₄ was uniformly dissolved in the films as promoted by hydroxypropyl cellulose (HPC). The mechanism of the Au particle formation was studied. It was found that HAuCl₄ was converted directly to Au metal particles upon contacting with H₂S gas. Au particles generated by this method were characterized with small particle size, sharp size distribution and high volume fraction in the films. The surface plasma resonance absorption of Au particles shifted to longer wavelength when TiO₂ component was introduced in the matrix.     

Cu + Au alloy particles formed in the underpotential deposition region of copper in acid solutions

Cu + Au alloy particles electrodeposited on an amorphous carbon electrode at the underpotential region of Cu in both perchloric acid and sulfuric acid solutions were investigated by means of transmission electron microscopy. The fraction of Cu in the Cu + Au alloy particles grown in both acid solutions with a concentration of 1 mM Au ion increased while the underpotential deposition (UPD) potential was decreased. However, it was independent of the concentration of Cu ion in solution. It is inferred that the composition of the Cu + Au alloy particles is dependent on the UPD potential. The fraction of Cu in the Cu + Au alloy particles grown at around the reversible Nernst potential of Cu in 0.1 mM HAuCl₄ + 50 mM Cu(ClO₄)₂ containing perchloric acid solution was 505. This result suggests a layer-by-layer formation of the Cu + Au alloy particles. The fraction of Cu in the Cu + Au alloy particles formed in the presence of sulfate was lower than that in the perchloric acid solution as the UPD potential and the concentration of Cu ion were the same. This is attributed to an influence of coadsorbed sulfate ions.     

Metallosurfactant Ionogels in Imidazolium and Protic Ionic Liquids as Precursors To Synthesize Nanoceria as Catalase Mimetics for the Catalytic Decomposition of H2O2

The gelation behavior of cationic surfactants with different counterions, Br^?, [FeCl₃Br]^?, and [CeCl₃Br]^?, in imidazolium ionic liquids (ILs) and protic ethylammonium nitrate was investigated. Small‐angle X‐ray scattering measurements and freeze‐fracture transmission electron microscopy observations revealed the lamellar phases of metallosurfactant ionogels. The characteristics of imidazolium ILs, including the size and type, have effects on metallosurfactant ionogel properties, such as transformation temperatures, interlayer spacing, and mechanical strength. Cubic fluorite structured cerium oxide nanoparticles (CeO₂ NPs) were produced by using metallosurfactant ionogels as precursors. Cubic fluorite CeO₂ exhibited good catalase mimetic activity toward H₂O₂ to generate O₂, providing more multiple mimetic enzyme activities of CeO₂ NPs for H₂O₂.     

Superparamagnetic POT/Fe3O4 nanoparticle composites with supported Au nanoparticles as recyclable high-performance nanocatalysts

A novel method has been developed to successfully synthesize Fe₃O₄ nanoparticles with tunable size and morphology supported on shells of poly(o-Toluidine)(POT) hollow microspheres. The as-prepared POT/Fe₃O₄ nanoparticle composites can be used as novel and magnetic-responsive catalyst supports to produce highly efficient and recyclable noble metal catalysts. The size of Fe₃O₄ nanoparticles supported on shells of POT hollow microspheres can be tuned from 4 to 12 nm by changing the concentration of Fe ions. The roles of the doping acid of POT and Zeta potentials of Fe₃O₄ nanoparticles and POT in the formation of the POT/Fe₃O₄ nanoparticle composites were discussed. Furthermore, gold nanoparticles that were supported on the as-synthesized POT/Fe₃O₄ nanoparticle composites have been achieved by utilizing the reactivity of POT towards Au ions. The size of gold nanoparticles can be tuned by altering the concentration of HAuCl₄. Finally, the catalytic activity of the obtained POT/Fe₃O₄/Au composites for 4-nitrophenol (4NP) reduction is investigated. The results demonstrate that such magnetic-responsive polymer-supported gold nanoparticles can be easily recovered and reused five times still remains high catalytic performance, which indicate their potential applications in the field of catalysis.     

The Hybrid of Gold Nanoparticles and 3D Flower‐like MnO2 Nanostructure with Enhanced Activity for Detection of Hydrogen Peroxide

3D Flower‐like manganese dioxide (MnO₂) nanostructure with the ability of catalysis for hydrogen peroxide (H₂O₂) and super large area that can support gold nanoparticles (AuNPs) with enhanced activity of electron transfer have been developed. The nanostructure of hybrids was prepared by directly mixing citric‐capped AuNPs and 3‐aminopropyltriethoxysilane (3‐APTES)‐capped nano‐MnO₂ using an electrostatic adsorption strategy. The Au‐MnO₂ composite was extensively characterized by scanning electron microscope (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), the Brunauer‐Emmett‐Teller (BET) method and X‐ray photoemission spectroscopy (XPS). Electrochemical properties were evaluated through cyclic voltammetry (CV) and amperometric method. The prepared sensor showed excellent electrochemical properties towards H₂O₂ with a wide linear range from 2.5×10⁻³∼1.39 mM and 3.89∼13.89 mM. The detection limit is 0.34 μM (S/N=3) with the sensitivities of 169.43 μA mM⁻¹ cm⁻² and 55.72 μA mM⁻¹ cm⁻². The detection of real samples was also studied. The result exhibited that the prepared sensor can be used for H₂O₂ detection in real samples.     

Gold photocatalysis in sustainable hydrogen peroxide generation

Hydrogen peroxide (H₂O₂) is a mild and green oxidant widely employed in organic syntheses, medical sector, disinfection, pulp bleaching, environmental remediation and biological processes. However, its production via the expensive, multistep and energy intensive anthraquinone process renders it less sustainable. Photocatalysis is a viable, sustainable and promising strategy to produce H₂O₂ from green sources: water and molecular O₂. This article presents key developments of photocatalytic H₂O₂ generation using gold (Au) nanoparticles supported on semiconductor photocatalysts. Several photocatalytic systems containing Au nanoparticles and the roles of Au nanoparticles in enhancing photocatalytic H₂O₂ generation including increasing the visible light absorption, facilitating the charge carrier separation and transfer, and as catalytic active sites are discussed. Factors defining the photocatalytic activity such as the effects of Au particle size and loading, localised surface plasmon resonance, mixed-gold component, and the design of photocatalysts are reviewed. Finally, the challenges and prospects for further developments of Au photocatalysis in sustainable H₂O₂ synthesis as well as other related applications are highlighted.     

Preparation of Au-TiO2 Hybrid Nano Particles in Silicate Film Made by Sol-Gel Method

TiO₂ nano particles with photo catalytic property were mixed with silica alkoxides solution with HAuCl₄/4H₂O. STS02 (purchased from Ishihara Sangyo Kaisha, Ltd.) was used as TiO₂ nano particles. The average size of TiO₂ nano particles was 7 nm in diameter. The gel film coated on glass substrate was heated and then HAuCl₄/4H₂O was thermally reduced at 390 degree. The coated silica gel film doped with HAuCl₄/4H₂O and TiO₂ nano particles was turned into light blue from colorless gel film after heat treatment. The optical absorption spectrum showed the absorption peak of the film heated at 390 degree shifted to at about 650 nm compare to SiO₂ film doped with Au nano particles without TiO₂ nano particles that had absorption peak at 542 nm. On the other hand, the film formed from coating solution incorporated TiAA (titanium tetraisopropoxide chelated by acetyl acetone) as TiO₂ source instead of TiO₂ nano particles had absorption peak at 550 nm. That means there was no effect on formation of Au nano particles when TiAA was incorporated. The average size of the particles was found to be about 23 nm in diameter by TEM observation. Furthermore EDX (Energy Dispersive X-ray Fluorescence Spectrometer) analysis of nano particles in the film indicated that Au-TiO₂ nano hybrid particles were formed. Simulation results also supported that the size in diameter of Au nano particles had little influence on the absorption coefficient of the silica film doped with Au nano particles.     

Real‐time Selective Detection of Hydrogen Peroxide Based on a Tantalum Deposited Pencil Lead Electrode for Evaluation of Enzyme Activities

In this study, we have carried out electrodeposition of tantalum (Ta) nanostructures on pencil lead electrode in non‐aqueous media at room temperature by applying a constant potential. The deposited Ta on pencil lead was examined for the catalytic effect regarding hydrogen peroxide (H₂O₂) reduction with voltammetry and amperometry. Ta/pencil lead electrode exhibited amperometric sensitivity of 0.317 μA mM⁻¹ cm⁻² and fast response time of 0.75 s, where selective detection of H₂O₂ was fulfilled without interruption from common electroactive biomaterials such as O₂, uric acid, ascorbic acid, dopamine, acetamidophenol, and glucose. For practical applications, the dynamic concentration changes of H₂O₂ during catalase and glucose oxidase‐involved reactions, either eliminating or producing H₂O₂, were successfully traced in real time with as‐prepared electrode. From the kinetics study for catalase and glucose oxidase, we evaluated Michaelis constants (K _m^app) as 7.8 mM for catalase and 37 mM for glucose oxidase, respectively.     

Generation of Methyl Vinyl Ketone from Oxidation of Levulinic Acid Oxidized by Cupric Oxide Complex

Methyl vinyl ketone (MVK) is a kind of high‐value chemical which has been widely used in many fields. In this paper, it is formed from oxidation of levulinic acid–a hydrolysis product of biomass. Copper oxide supported on cerium dioxide (CuO/CeO₂) and alumina (CuO/Al₂O₃) were prepared and used for the oxidation of levulinic acid (LA). The oxidants were characterized by means of X‐ray diffraction (XRD), H₂‐temperature programmed reduction (H₂‐TPR) and atomic force microscope (AFM) techniques. CuO/CeO₂ and CuO/Al₂O₃ show a different behavior with respect to pure CuO. The experiments revealed that CuO/CeO₂ and CuO/Al₂O₃ can oxidize LA and get methyl vinyl ketone [yield of 15.5% detected by head space‐gas chromatograph‐mass spectrometer (HS‐GC‐MS)] under mild reactive conditions, while pure CuO oxidizes LA to produce butanone (MEK).     

A netlike DNA-templated Au nanoconjugate as the matrix of the direct electrochemistry of horseradish peroxidase

Herein, a novel DNA-templated Au nanoparticles (Au-DNA) nanoconjugate was prepared by using the combination of metallization and DNA compaction. The electrostatic interaction between Au(Ш) and the phosphate backbone of DNA formed the netlike coordination compound of Au(Ш)-DNA, and then the complex was chemically reduced to form Au nanoparticles in this network-like DNA conformation. The negatively charged nanoconjugate was used as the matrix for immobilization of horseradish peroxidase (HRP). A stable and well-defined redox peaks of HRP were observed on the Au-DNA nanoconjugate modified glassy carbon (GC) electrode, which indicated that the modified enzyme electrode displayed good direct electron transfer behavior and excellent reducing ability toward hydrogen peroxide (H₂O₂) with the apparent Michaelis–Menten constant (K_m) estimated to be 0.147 mM.     

CO oxidation over Au/CeO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> catalists: The effect of the support composition of the au-support interaction

The effect of the support composition on the Au-support interactions and its role in the creation of the activity of Au/CeO₂-ZrO₂ catalysts in CO oxidation has been studied. The CeO₂-ZrO₂ oxides and Au/CeO₂-ZrO₂ catalysts were synthesized, characterized by BET, XRD, HRTEM, AAS, TPR-H₂, and tested in CO oxidation. An approximate evaluation of the H₂ consumption for the surface reduction of the studied samples was estimated applying the model developed by Johnson and Mooi, which is based on the qualitative relationship between the amount of the capping oxygen and BET surface area. The sequence of the increasing percentage of O₂ atoms in the capping peak to the total Ce atoms follows the sequence of the decreasing Zr/Ce molar ratio in the sample. The activity of Au/CeO₂-ZrO₂ catalysts depends on the support composition and increases with the decrease in Zr/Ce molar ratio.     

Controllable preparation and properties of composite materials based on ceria nanoparticles and carbon nanotubes

We report a method to prepare composites based on carbon nanotubes (CNTs) and CeO₂ nanoparticles (NPs). The CeO₂ NPs were attached to CNTs by hydrothermal treatment of Ce(OH)₄/CNT mixture in NaOH solution at 180 °C. It was found that larger CeO₂ NPs were formed in the presence of CNTs. Grain size of CeO₂ NPs in the composites can be reduced when NaNO₃ was added in the hydrothermal process. Electrochemical characterizations have shown that the composites possess a specific capacity between those of CNTs and CNTs mechanically mixed with CeO₂. These CeO₂/CNT composites could serve as promising anode materials for Li-ion batteries.