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Butynediol (2-Butyne-1,4-diol), a well-known type-II brightening additive, changes the interfacial pH resulting in the formation of porous cobalt hydroxide film of ca. 1 µm thickness over the copper substrate in a short duration of electrodeposition (2 min) and at a very low current density (-5 mA cm-2) from sulfate bath. In the absence of butynediol, a metallic cobalt layer was observed under identical deposition conditions. The choice of anions (sulfates, chlorides and nitrates) in the electrodeposition bath determines the kind of electrodeposited films obtained, viz., cobalt, cobalt/cobalt hydroxide, and compact cobalt hydroxide. The adsorption of butynediol enhances hydrogen evolution due to water reduction that facilitates the formation of porous microstructures of cobalt hydroxide. Competition for adsorption sites between butynediol and chloride and dissolution of cobalt hydroxide by diffusing protons result in a mixed metallic cobalt particle and porous cobalt hydroxide microstructure. The variations in the phases and microstructures of electrodeposits were evidenced through the difference in the magnetic and electrocatalytic properties. [ABSTRACT FROM AUTHOR]

The study presents the first example of an adsorbed carbon monoxide (CO) enabled self-terminated Au-grafting on triphenylphosphine (PPh 3 ) stabilized Pt 6 nanoclusters (NCs) (Pt 6 (PPh 3 ) 4 Cl 5 NCs or Pt 6 NCs). Adsorbed PPh 3 ligands weaken the Pt-CO bond enabling the self-terminated Au-grafting on Pt 6 NCs. The Au-grafted Pt 6 NCs exhibit enhanced methanol electrooxidation (MOR) in acidic solutions. The surface is composed of a PtAu ensemble exhibiting enhanced MOR and CO tolerance due to the synergistic interaction of Pt with Au and PPh 3 . The hydrogen underpotential deposition (H-UPD) signal from a CO-covered surface reveals the existence of free-Pt sites on the PtAu ensemble causing higher MOR reactivity. The Au and PPh 3 ensure electrocatalytic activity of the NCs, depriving of them at anodic potentials results in "a death-valley" trend., (© 2024 Wiley‐VCH GmbH.)

A robust hydrogen evolution is demonstrated from Au 25 (PET) 18 ] - nanoclusters (PET = 2-phenylethanethiol) grafted with minimal platinum atoms. The fabrication involves an electrochemical activation of nanoclusters by partial removal of thiols, without affecting the metallic core, which exposes Au-sites adsorbed with hydrogen and enables an electroless grafting of platinum. The exposed Au-sites feature the (111)-facet of the fcc-Au 25 nanoclusters as assessed through lead underpotential deposition. The electrochemically activated nanoclusters (without Pt loading) show better electrocatalytic reactivity toward hydrogen evolution reaction than the pristine nanoclusters in an acidic medium. The platinum-grafted nanocluster outperformed with a lower overpotential of 0.117 V vs RHE (RHE = Reversible Hydrogen Electrode) compared to electrochemically activated nanoclusters (0.353 V vs RHE ) at 10 mA cm -2 and is comparable with commercial Pt/C. The electrochemically activated nanoclusters show better reactivity at higher current density owing to the ease of hydrogen release from the active sites. The modified nanoclusters show unique supramolecular self-assembly characteristics as observed in electron microscopy and tomography due to the possible metallophilic interactions. These results suggest that the post-surface modification of nanoclusters will be an ideal tool to address the sustainable production of green hydrogen., (© 2023 Wiley‐VCH GmbH.)

Atomically precise nanoclusters (NCs) have recently emerged as ideal building blocks for constructing self-assembled multifunctional superstructures. The existing structures are based on various non-covalent interactions of the ligands on the NC surface, resulting in inter-NC interactions. Despite recent demonstrations on light-induced reversible self-assembly, long-range reversible self-assembly based on dynamic covalent chemistry on the NC surface has yet to be investigated. Here, it is shown that Au 25 NCs containing thiolated umbelliferone (7-hydroxycoumarin) ligands allow [2+2] photocycloaddition reaction-induced self-assembly into colloidal-level toroids. The toroids upon further irradiation undergo inter-toroidal reaction resulting in macroscopic supertoroidal honey-comb frameworks. Systematic investigation using electron microscopy, atomic force microscopy (AFM), and electron tomography (ET) suggest that the NCs initially form spherical aggregates. The spherical structures further undergo fusion resulting in toroid formation. Finally, the toroids fuse into macroscopic honeycomb frameworks. As a proof-of-concept, a cross-photocycloaddition reaction between coumarin-tethered NCs and an anticancer drug (5-fluorouracil) is demonstrated as a model photo-controlled drug release system. The model system allows systematic loading and unloading of the drug during the assembly and disassembly under two different wavelengths. The results suggest that the dynamic covalent chemistry on the NC surface offers a facile route for hierarchical multifunctional frameworks and photocontrolled drug release., (© 2023 Wiley-VCH GmbH.)

In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.

Hydroxyl radicals arising from the Fenton reagent remove metastable surface gold atoms (low coordinated high-energy surface atoms) on the Au surface, thus precluding the formation of stable oxides. The resultant smooth surface, upon hydroxyl-radical activation, electrocatalyzes oxygen evolution reaction in 0.1 M NaOH at overpotentials lowered by 190 mV @ 10 mA cm(-2).

Gradual, yet a great leap: electrosynthesized surfactant-stabilized gold atomic clusters (AuACs; Au(n) , 5≤n≤13) electrocatalyze the oxygen reduction reaction (ORR) in acid solution at low overpotentials. Depending on the surfactant concentration, the ORR mechanism gradually transits from a direct four-electron to a two-electron pathway (see picture; SHE=standard hydrogen electrode), which suggests the transformation of atomic clusters into nanoparticles., (Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)