RESUMEN
Chirality on the molecular or nanometer scale is particularly significant in chemistry, materials science, and biomedicine. Chiral electrochemical reactions on solid surfaces are currently a hot research topic. Herein, a chiral solid surface is constructed in aqueous solutions by mixing chiral molecules, d- and l-glutamic, with γ-Fe2O3 and Fe3O4 nanoparticles (NPs) and MnFe2O4 colloidal nanocrystal assembly (CNA). Cyclic voltammetry and differential pulse voltammetry measurements are conducted in a phosphate buffer solution (PBS) containing ascorbic acid (AA) or isoascorbic acid (IAA), and a chiral effect appears on the electroreduction of ferric ions of amino acid-modified magnetic samples. A negative or positive potential shift is observed, respectively, for magnetic structures modified by l- and d-glutamic acid in aqueous AA electrolyte, while the opposite is observed for these samples in IAA electrolyte. The reduction peak current increases by 0.8-1.2 times for the electrodes modified with l- and d-glutamate molecules, improving the electron transport efficiency. The chiral effect is absent when the electrolytes contain achiral uric acid or dopamine, or even chiral l-/d-/ld-tartaric acid. The chiral recognition between d-/l-glutamic acid and AA/IAA at the electrochemical interface is suggested to be related to their spinal configurations. These observations will be helpful for the rational design of inorganic functional chiral micro/nanostructures.
RESUMEN
Two-dimensional (2D) nanostructured catalysts have attracted great attention in many important fields, including energy applications and chemical industry. In this study, PdCu nanosheet assemblies (NSAs) have been synthesized and investigated as electrocatalysts for direct ethanol fuel cells in an alkaline medium. A great number of active sites on the nanosheets of PdCu NSAs for ethanol electro-oxidation are exposed, where the electron structures are optimized combined with the second element copper. Electrochemical measurements show that PdCu NSA1 exhibits excellent catalytic activity (2536 mA mg-1) and cyclic stability compared to PdCu NSA2 (1700 mA mg-1) and PdCu NSA3 (1436 mA mg-1), much higher than commercial Pd/C. Kinetics studies on the electrolysis of ethanol suggest that PdCu NSAs should be more favorable at higher catalytic temperatures, higher concentrations of ethanol, and low pH value environments. The unique composition and structures PdCu NSA1 would result in the lowest energy barrier in the rate-controlling step of the ethanol oxidation reaction (EOR), confirmed by density functional theory (DFT). The formation mechanism of PdCu NSAs and their excellent electrocatalytic activity toward EOR have been discussed and analyzed.
RESUMEN
Although many researchers have made great efforts to pursue promising high-efficiency electrocatalysts, a formidable challenge remains for designing excellent palladium-based electrocatalysts for commercializing direct liquid fuel cells. This study reports the synthesis of bimetallic PdPb nanoparticles (NPs) via a mixed solution containing cetyl trimethyl ammonium bromide as the capping agent. Alloyed PdPb NPs are formed, where the size of the NPs increases as Pb atoms are introduced gradually. However, Pd3Pb NPs are obtained with the same molar ratio of Pd and Pb in the raw systems. Among all of the as-made NPs, Pd9Pb1 NPs exhibit superior catalytic activity (2620 mA mg-1) toward ethanol electrooxidation, 4.3 times higher than commercial Pd/C catalysts (613 mA mg-1). The overall rate of the EOR for PdPb NPs is determined, demonstrating that the electrocatalytic activity of the PdPb NPs increases at high catalytic temperatures, in high pH environments, and/or at high ethanol concentrations.
RESUMEN
Synthesizing alloyed bimetallic electrocatalysts with a three-dimensional (3D) structure assembly have arouse great interests in electrocatalysis. We synthesized a class of alloyed Pd3Pb/Pd nanosheet assemblies (NSAs) composed of a two-dimensional (2D) sheet structure with adjustable compositions via an oil bath approach at a low temperature. Both the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images reveal the successful formation of the nanosheet structure, where the morphology of Pd3Pb/Pd NSAs can be regulated by adjusting the atomic mole ratio of Pb and Pb metal precursors. The power X-ray diffraction (XRD) pattern shows that Pd3Pb/Pd NSA catalysts are homogeneously alloyed. Electrochemical analysis and the density functional theory (DFT) method demonstrate that the electrocatalytic activity of the alloyed Pd3Pb/Pd NSAs can be improved by the doping of the Pb element. As a result of the addition of element Pb and change of the electron structure, the electrocatalytic activity toward ethanol oxidation of alloyed Pd3Pb/Pd-15 NSA can reach up to 2886 mA mg-1, which is approximately 2.8 times that of the pure Pd NSA counterpart (1020 mA mg-1). The Pd3Pb/Pd NSAs are favorable in a high catalytic temperature, high KOH concentration, and high ethanol concentration.
RESUMEN
Black phosphorus is a two-dimensional layer material with promising applications due to its many excellent physicochemical properties, including high carrier mobility, ambipolar field effect and unusual in-plane anisotropy. Currently, BP has been widely used in biomedical engineering, photocatalysis, semiconductor devices, and energy storage electrode materials. However, the unique structure of BP makes it highly chemically active, leading to its easy oxidation and degradation in air, which limits its practical applications. Recently, researchers have proposed a number of initiatives that can address the environmental instability of BP, and the application of these physical and chemical passivation techniques can effectively enhance the environmental stability of BP, including four modification methods: covalent functionalization, non-covalent functionalization, surface coordination, physical encapsulation and edge passivation. This review highlights the mechanisms of the above modification techniques in addressing the severe instability of BP in different application scenarios, as well as the advantages and disadvantages of each method. This review can provide guidance for more researchers in studying the marvellous properties of BP and accelerate the practical application of BP in different fields.
RESUMEN
The synthesis of metal nanometer electrocatalysts with a two-dimensional (2D) structure or rich active sites has become a research hotspot in electrocatalysis. In this work, surfactant hexadecyltrimethylammonium bromide (CTAB) was used to assist the synthesis and assembly of Pd ultrathin nanosheet with the help of Mo(CO)6 in the start system. Pd nanochain composed of nanoparticles is obtained under the same condition, replacing CTAB with carrageenan only. Electrochemical measurements showed that the catalytic peak current density for the electrooxidation of ethanol can reach 2145 mA mg-1 for the Pd nanosheet assembly (NSA) and 1696 mA mg-1 for Pd nanochains. Pd nanosheet assembly also has a lower electron-transfer barrier, better catalytic stability, and antipoisoning performance than that of Pd nanochains. The mechanism of Pd nanosheets and nanochains catalysts the enhanced electrocatalytic activity toward ethanol oxidation has been discussed based on the experimental data.