Galvanic Replacement of Electrochemically Restructured Copper Electrodes with Gold and Its Electrocatalytic Activity for Nitrate Ion Reduction

The electrochemical formation of nanostructured materials is a cost effective route to creating substrates that can be employed in a variety of applications. In this work the surface of a copper electrode was electrochemically restructured in an alkaline solution containing ethanol as an additive to modify the surface morphology, and generate a Cu/Cu2O surface, which is known to be active for the electrocatalytic reduction of environmentally harmful nitrate ions. To increase the activity of the nanostructured surface it was decorated with gold prisms through a facile galvanic replacement approach to create an active Cu/Cu2O/Au layer. The surface was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, as well as electrochemical techniques. It was found that the presence of recalcitrant oxides, and Au was beneficial for the increased activity compared to unmodified copper and undecorated restructured copper and was consistent with the incipient hydrous oxide adatom mediator model of electrocatalysis. This approach to generating nanostructured metal/metal oxide surfaces that can be galvanically replaced to create these types of composites may have other applications in the area of electrocatalysis

Liquid metal assisted sonocatalytic degradation of organic azo dyes to solid carbon particles

Room temperature liquid metals are an emerging class of materials for a variety of heterogeneous catalytic reactions. In this work we explore the use of Ga based liquid metals as a sonochemical catalyst for the degradation of organic azo dyes such as methyl orange, congo red and eriochrome black T. Rapid degradation to non toxic solid carbon particles was achieved over a large dye concentration range to produce differently sized particlesviaboth bath and probe sonication which could be repeated multiple times with the same catalyst.</p

Electrochemical Formation of Amorphous Molybdenum Phosphosulfide for Enabling the Hydrogen Evolution Reaction in Alkaline and Acidic Media

The formation of a nonprecious metal catalyst that is active for the hydrogen evolution reaction (HER) over a wide pH range is of particular interest. In this work, a mixed anion electrocatalyst, namely, amorphous molybdenum phosphosulfide films containing oxygen were produced via a simple electrochemical process allowing the composition and morphology of the film to be controlled. The catalyst shows a homogeneous distribution of Mo, S, P, and O with a high number of active sites due to its amorphous state. (NH₄)₂MoS₄ was used as a molybdenum and sulfur source, while NaPO₂H₂ was used as the phosphorus source. Thiourea was also investigated as an additional sulfur source during the electrodeposition process. The electrocatalyst was active for the HER in acidic media as expected, but showed excellent performance in alkaline media where Tafel slope values of 36 and 122 mV dec^–1 were recorded, respectively. In addition, the electrocatalyst demonstrated long-term stability in both media for several hours. The materials were characterized using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), and their physicochemical properties correlated to their electrocatalytic activity for the HER

Room Temperature Electrochemical Synthesis of Crystalline GaOOH Nanoparticles from Expanding Liquid Metals

Gallium oxyhydroxide (GaOOH) is a wide band gap semiconductor of interest for a variety of applications in electronics and catalysis where the synthesis of the crystalline form is usually achieved via hydrothermal routes. Here we synthesize GaOOH via the electrochemical oxidation of gallium based liquid metals in solutions of 0.1 M NaNO₃ electrolyte with pH adjusted over the range of 7–8.4 with NaOH. This electrochemical approach employed under ambient conditions results in the formation of crystalline oblong shaped α-GaOOH nanoparticles from both liquid gallium and liquid galinstan which is a eutectic based on Ga, In, and Sn. The size and shape of the GaOOH particles could be controlled by the solution pH. The product is characterized with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV–visible spectroscopy, and photoluminescence spectroscopy. During the electrochemical oxidation process, the liquid metal drop was found to expand significantly in the case of galinstan due to a constant electrowetting effect which resulted in the continuous expulsion of nanomaterial from the expanding liquid metal droplet. This electrochemical approach may be applicable to other liquid metals for the fabrication of metal oxide nanomaterials and also demonstrates that significant chemical reactions may be occurring at the surface of liquid metals that are actuated under an applied electric field in aqueous electrolytes

Electrochemical Tailoring of Fibrous Polyaniline and Electroless Decoration with Gold and Platinum Nanoparticles

Presented in this work is a facile and quick electrochemical method for controlling the morphology of thick polyaniline (PANi) films, without the use of templates. By stepping the polymerization potential from high voltages to a lower (or series of lower) voltage(s), we successfully controlled the morphology of the polymer, and fibrous structures, unique to each potential step, were achieved. In addition, the resultant film was tested electrochemically for its viability as an electrode material for flexible batteries and supercapacitors. Furthermore, the PANi film was decorated with gold and platinum nanoparticles via an electroless deposition process for possible electrocatalytic applications, whereby the oxidation of hydrazine at the composite was investigated

Theoretical Evaluation of Highly Efficient Nitrate Reduction to Ammonia on InBi

Electrocatalytic reduction of nitrate to ammonia has become a popular approach for wastewater treatment and ammonia production. However, the development of highly efficient electrocatalysts remains a great challenge. Herein, we systematically studied the potential of InBi for nitrate reduction to ammonia (NRA) based on density functional theory (DFT) calculations. Our results reveal that InBi exhibits high activity for NRA via an O-end pathway, where the free energy evolution of all intermediates is downhill in the most favorable elementary steps. The activation of nitrate originates from the strong orbital hybridization between oxygen and indium atoms, leading to an enhanced charge transfer as well as NO3- adsorption. In particular, the competing hydrogen evolution reaction (HER) is effectively suppressed due to the weak adsorption of proton. Our study not only proves the great electrocatalytic potential of InBi as a novel catalyst for NRA but also points out a new way to design NRA electrocatalysts for practical applications.</p

Synthesis of CuTCNQ/Au Microrods by Galvanic Replacement of Semiconducting Phase I CuTCNQ with KAuBr₄ in Aqueous Medium

The spontaneous reaction between microrods of an organic semiconductor molecule, copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with [AuBr₄]⁻ ions in an aqueous environment is reported. The reaction is found to be redox in nature which proceeds via a complex galvanic replacement mechanism, wherein the surface of the CuTCNQ microrods is replaced with metallic gold nanoparticles. Unlike previous reactions reported in acetonitrile, the galvanic replacement reaction in aqueous solution proceeds via an entirely different reaction mechanism, wherein a cyclical reaction mechanism involving continuous regeneration of CuTCNQ consumed during the galvanic replacement reaction occurs in parallel with the galvanic replacement reaction. This results in the driving force of the galvanic replacement reaction in aqueous medium being largely dependent on the availability of [AuBr₄]⁻ ions during the reaction. Therefore, this study highlights the importance of the choice of an appropriate solvent during galvanic replacement reactions, which can significantly impact upon the reaction mechanism. The reaction progress with respect to different gold salt concentration was monitored using Fourier transform infrared (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS), as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were also investigated for their potential photocatalytic properties, wherein the destruction of the organic dye, Congo red, in a simulated solar light environment was found to be largely dependent on the degree of gold nanoparticle surface coverage. The approach reported here opens up new possibilities of decorating metal–organic charge transfer complexes with a host of metals, leading to potentially novel applications in catalysis and sensing