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This study presents a green, ultra‐fast, and facile technique for the fabrication of micro/nano‐structured and porous Cu electrodes through in‐liquid plasma electrolysis using phosphorous‐oxoanion‐based electrolytes. Besides the preferential surface faceting, the Cu electrodes exhibit unique surface structures, including octahedral nanocrystals besides nanoporous and microporous structures, depending on the employed electrolyte. The incorporation of P‐atoms into the Cu surfaces is observed. The modified Cu electrodes display increased roughness, leading to higher current densities for CO2 electroreduction reaction. The selectivity of the modified Cu electrodes towards C2 products is highest for the Cu electrodes treated in Na2HPO3 and Na3PO4 electrolytes, whereas those treated in Na2H2PO2 produce the most H2. The Cu electrode treated in Na3PO4 produces ethylene (23 %) at −1.1 V vs. RHE, and a comparable amount of acetaldehyde (15 %) that is typically observed for Cu(110) single crystals. The enhanced selectivity is attributed to several factors, including the surface morphology, the incorporation of phosphorus into the Cu structure, and the formation of Cu(110) facets. Our results not only advance our understanding of the influence of the electrolyte's nature on the plasma electrolysis of Cu electrodes, but also underscores the potential of in‐liquid plasma treatment for developing efficient Cu electrocatalysts for sustainable CO2 conversion. [ABSTRACT FROM AUTHOR]

Several electrochemical conversion reactions occur under high cathodic currents, where electrocatalysts can experience substantial alterations in their surface structure through cathodic corrosion, influencing their electrocatalytic performance. Thus, understanding the structural changes of metal surfaces upon cathodic polarization is crucial for the rational design of active and stable electrocatalysts in the context of a transition towards green technologies. In this work, we probe the structural changes of Au surfaces after cathodic corrosion in 10 M NaOH and 10 M KOH at different potentials, using metal deposition and electrocatalytic surface-sensitive reactions. Cathodic polarization increases the electrochemically active surface area and alters the distribution of crystal facets, as evidenced by underpotential deposition of Pb and the electrochemical behaviour in 0.1 M H2SO4. The Au electrode surfaces obtained in NaOH and KOH exhibit different distributions and sizes of (111)-facets. The electrocatalytic activity of the restructured Au electrodes towards the formic acid oxidation reaction (FAOR) and the hydrogen evolution reaction (HER) is evaluated. The nanostructured Au electrodes obtained after polarization in NaOH show superior HER activity compared to those obtained in KOH, which is related to the formed nanostructures and the influence of low-coordination sites. Furthermore, the FAOR activity of the Au electrodes with higher (111)-contribution, achieved through polarization in 10 M KOH, is comparable to well-ordered Au(111) single crystals, emphasizing the key role of terraces in FAOR rather than surface steps as active sites responsible for the extraordinary HER activity. To further explore the electrocatalytic performance, we demonstrate the electrochemical fabrication of Pd–Au bimetallic nanostructures with varying contributions of (111)-facets, obtained through a combination of cathodic corrosion and electrodeposition. Remarkably, the electrocatalytic activity of Pd films on nanostructured Au electrodes towards FAOR in HClO4 and H2SO4 solutions is significantly enhanced compared to as-polished Au electrodes and is dependent on the contribution of (111)-facets. The present findings are relevant to the stability and long-term performance of cathodes in a variety of applications including electrosynthesis. [ABSTRACT FROM AUTHOR]

Cathodic corrosion is an electrochemical process that induces restructuring, roughening, and etching of metal surfaces at a highly negative surface charge density, yet, details of the reaction mechanism are not fully resolved. An in‐depth fundamental understanding of the processes and parameters underlying cathodic corrosion is crucial for tailoring the surface structure of the metal electrodes and for synthesizing shape‐ and size‐controlled nanoparticles. Here, we investigate the relevance of water and hydrogen evolution in the cathodic corrosion process. To achieve this aim, Au electrodes were polarized at ‐1.6 V versus RHE in KOH and NaOH electrolytes prepared using different water + methanol mixtures. Structural changes of the Au surfaces were studied by cyclic voltammetry and monitored by scanning electron microscopy (SEM). Most importantly, cathodic corrosion does not take place in the absence of water. There is no detectable bubble formation due to the hydrogen evolution reaction on Au in purely methanolic alkali. Furthermore, the electrochemically active surface area, facet distribution, and surface morphology of Au electrodes are significantly altered upon cathodic polarization as a function of the water concentration. Cathodic corrosion features become more and more pronounced with a further increase in water content. In addition, substantial differences in the surface structure of Au are observed as a function of the nature and concentration of alkali metal cations. Overall, this study provides a more detailed understanding of the role of water and the hydrogen evolution reaction in dominating cathodic corrosion, which might advance the understanding of this phenomenon. [ABSTRACT FROM AUTHOR]

This article in ChemCatChem explores the effect of different alkali metal cations on the cathodic corrosion of gold electrode surfaces. The study found that polarizing gold at highly negative potentials resulted in various structures, such as nanoporous surfaces with CsOH, spherical nanoparticles and triangular pits with KOH, octahedral nanocrystals with NaOH, and triangular pits with LiOH. The research also emphasized the importance of electrolyte purity, as trace iron and nickel impurities in CsOH were found to significantly impact cathodic corrosion. The full details of the study can be found in the Research Article by Mohamed M. Elnagar, Ludwig A. Kibler, and Timo Jacob. [Extracted from the article]

A robust and efficient route to modify the chemical and physical properties of polycrystalline copper (Cu) wires via versatile plasma electrolysis is presented. Silica (SiO2) nanoparticles (11 nm) are introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these SiO2 nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral‐like microstructures are observed by scanning electron microscopy on the Cu surface after the in‐liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of CuO as a thin outer layer and a significant amount of inner Cu2O. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral‐like microstructures by a simple electrochemical treatment. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of Ru (II) terpyridine complexes derived from 4′ functionalized 2,2′:6′,2″‐terpyridine (tpy) ligands are reported. The heteroleptic complexes comprise the synthesized ligands 4′‐(2‐thienyl)‐ 2,2′:6′,2″‐terpyridine) or (4′‐(3,4‐dimethoxyphenyl)‐2,2′:6′,2″‐terpyridine and (dimethyl 5‐(pyrimidin‐5‐yl)isophthalate). The new complexes [Ru(4′‐(2‐thienyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)Cl2] (9), [Ru(4′‐(3,4‐dimethoxyphenyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)Cl2] (10), and [Ru(4′‐(2‐thienyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)(NCS)2] (11) were characterized by 1H‐ and 13C‐NMR spectroscopy, C, H, N, and S elemental analysis, UPLC‐ESI‐MS, TGA, FT‐IR, and UV‐Vis spectroscopy. The biological activities of the synthesized ligands and their Ru (II) complexes as anti‐inflammatory, antimicrobial, and anticancer agents were evaluated. Furthermore, the toxicity of the synthesized compounds was studied and compared with the standard drugs, namely, diclofenac potassium and ibuprofen, using hemolysis assay. The results indicated that the ligands and the complex 9 possess superior anti‐inflammatory activities inhibiting albumin denaturation (89.88–100%) compared with the standard drugs (51.5–88.37%) at a concentration of 500 μg g−1. These activities were related to the presence of the chelating N‐atoms in the ligands and the exchangeable chloro‐ groups in the complex. Moreover, the chloro‐ and thiophene groups in complex 9 produce a higher anticancer activity compared with its isothiocyanate derivative in the complex 11 and the 3,4‐dimethoxyphenyl moiety in complex 10. Considering the toxicity results, the synthesized ligands are nontoxic or far less toxic compared with the standard drugs and the metal complexes. Therefore, these newly synthesized compounds are promising anti‐inflammatory agents in addition to their moderate unique broad antimicrobial activity. [ABSTRACT FROM AUTHOR]

The quality of emission spectra of metal complexes gives good insights into their performance in many optoelectronic applications. Herein, the effect of the number and position of various ligand structures on the emission spectra of Ru bipyridine complexes was studied. Specifically, the use of a different number of withdrawing groups (COOH) was investigated in detail. The complexes were first investigated using density functional theory (DFT) and time‐dependent DFT calculations and then confirmed experimentally. The bandgap energy, reactivity, emission spectra and Stokes shift were found to depend on the number and position of the withdrawing groups attached to the Ru(bpy)22+ complexes. Upon increasing the number of withdrawing groups, the electrons were found to be withdrawn from the carbon orbitals and resonated to reach the metal, and accumulated around it, thus enhancing the metal‐to‐ligand charge transfer mechanism instead of the ligand‐to‐ligand charge transfer mechanism. The complexes with more withdrawing groups showed spectra with more intense emission peaks with shorter lifetime, indicating the enhancement in the photoactivity of the complexes. Ligands with ring nitrogens with two COOH groups showed the greatest effect on the enhancement of the emission spectra with a lifetime of 0.5359 ns. The resulting collective emission spectra covered a wide wavelength range, making the investigated complexes a good choice for many optoelectronic applications. Ru(II) complexes with various electron‐withdrawing ligands were studied. It was predicted computationally that the greater the number of added electron‐withdrawing groups, the better would be the emission performance. Experimental measurements showed that the greater the number of inserted ring nitrogens, the shorter the lifetime and the more intense the emission will be. A mixture of the studied complexes showed wide emission range covering from the beginning of the green to the end of the visible region. [ABSTRACT FROM AUTHOR]

Ruthenium complexes incorporating 2,2' : 6',2''-terpyridine ligands have emerged as promising candidates due to their versatile biological activities including DNA-binding, anti-inflammatory, antimicrobial, and anticancer properties. In this study, three new 4'-functionalized bis(terpyridine) Ru(II) complexes were synthesized. These complexes feature one ligand as 4-(2,2' : 6',2''-terpyridine-4'-yl) benzoic acid and the second ligand as either 4'-(2-thienyl)-2,2' : 6',2''-terpyridine, 4'-(3,4-dimethoxyphenyl)-2,2' : 6',2''-terpyridine, or 4'-(4-dimethylaminophenyl)-2,2' : 6',2''-terpyridine. Besides the chemical characterization by 1 H and 13 C NMR, mass spectrometry, and absorption and emission spectroscopy, the complexes were tested for their biological activity as anti-inflammatory, anticancer, and antimicrobial agents. Moreover, the toxicity of the Ru(II) complexes was assessed and benchmarked against diclofenac potassium and ibuprofen using a haemolysis assay. Biological evaluations demonstrate that these ruthenium complexes exhibit promising therapeutic potential with reduced haemolytic activity compared to standard drugs. They demonstrate substantial anti-inflammatory effects through inhibition of albumin denaturation along with moderate cytotoxicity against cancer cell lines and broad-spectrum antimicrobial activity. These findings highlight the multifaceted biomedical applications of 4'-functionalized bis(terpyridine) Ru(II) complexes, suggesting their potential for further development as effective and safe therapeutic agents., (© 2024 Wiley-VCH GmbH.)

This study presents a green, ultra-fast, and facile technique for the fabrication of micro/nano-structured and porous Cu electrodes through in-liquid plasma electrolysis using phosphorous-oxoanion-based electrolytes. Besides the preferential surface faceting, the Cu electrodes exhibit unique surface structures, including octahedral nanocrystals besides nanoporous and microporous structures, depending on the employed electrolyte. The incorporation of P-atoms into the Cu surfaces is observed. The modified Cu electrodes display increased roughness, leading to higher current densities for CO 2 electroreduction reaction. The selectivity of the modified Cu electrodes towards C 2 products is highest for the Cu electrodes treated in Na 2 HPO 3 and Na 3 PO 4 electrolytes, whereas those treated in Na 2 H 2 PO 2 produce the most H 2 . The Cu electrode treated in Na 3 PO 4 produces ethylene (23 %) at -1.1 V vs. RHE, and a comparable amount of acetaldehyde (15 %) that is typically observed for Cu(110) single crystals. The enhanced selectivity is attributed to several factors, including the surface morphology, the incorporation of phosphorus into the Cu structure, and the formation of Cu(110) facets. Our results not only advance our understanding of the influence of the electrolyte's nature on the plasma electrolysis of Cu electrodes, but also underscores the potential of in-liquid plasma treatment for developing efficient Cu electrocatalysts for sustainable CO 2 conversion., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)