RESUMO
The designing of efficient electrocatalysts for hydrogen generation is essential for the practical application of water-splitting devices. With numerous electrochemical advantages, transition metal sulphides are regarded as the most promising candidates for catalysing the hydrogen evolution reaction (HER) in acidic media. In the present study, Ru-doped cobalt sulphide nanosheets, termed Co9S8/Ru@t (t = 24 h, 48 h, and 72 h), were obtained by varying the reaction time from 24 h to 72 h from a RuCo-PBA precursor. The role of the time period for the synthesis of Co9S8/Ru@48h is vital in increasing the number of electroactive sites and optimising the hydrogen adsorption-desorption phenomena leading to an increment in the HER activity. The electrochemical outcomes demonstrate that the optimized Co9S8/Ru@48h requires a low overpotential of just 94 mV to produce 10 mA cm-2 current density, and also exhibits a lower Tafel slope value of 84 mV dec-1 defining its faster reaction kinetics. The as-synthesized Co9S8/Ru@48h was stable for up to 20 h of constant electrolysis signifying its outstanding durability. The optimized synthetic approach and impressive electrochemical results make Co9S8/Ru@48h a suitable alternative to noble-metal-based electrocatalysts for the HER.
RESUMO
In this research article, two multicopper [Cu3] and [Cu6] clusters, [Cu3(cpdp)(µ3-SO4)(Cl)(H2O)2]·3H2O (1) and [Cu6(cpdp)2(µ2-O)(Cl)2(H2O)4]·2Cl (2) (H3cpdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol), have been explored as potent antibacterial and antibiofilm agents. Their molecular structures have been determined by a single-crystal X-ray diffraction study, and the compositions have been established by thermal and elemental analyses, including electrospray ionization mass spectrometry. Structural analysis shows that the metallic core of 1 is composed of a trinuclear [Cu3] assembly encapsulating a µ3-SO42- group, whereas the structure of 2 represents a hexanuclear [Cu6] assembly in which two trinuclear [Cu3] motifs are exclusively bridged by a linear µ2-O2- group. The most striking feature of the structure of 2 is the occurrence of an unusual linear oxido-bridge, with the Cu3-O6-Cu3' bridging angle being 180.00°. Whereas 1 can be viewed as an example of a copper(II)-based compound displaying a rare µ3:η1:η1:η1 bridging mode of the SO42- group, 2 is the first example of any copper(II)-based compound showing an unsupported linear Cu-O-Cu oxido-bridge. Employing variable-temperature SQUID magnetometry, the magnetic susceptibility data were measured and analyzed exemplarily for 1 in the temperature range of 2-300 K, revealing the occurrence of antiferromagnetic interactions among the paramagnetic copper centers. Both 1 and 2 exhibited potent antibacterial and antibiofilm activities against methicillin-resistant Staphylococcus aureus (MRSA BAA1717) and the clinically isolated culture of methicillin-resistant S. aureus (MRSA CI1). The mechanism of antibacterial and antibiofilm activities of these multicopper clusters was investigated by analyzing and determining the intracellular reactive oxygen species (ROS) generation, lipid peroxidation, microscopic observation of cell membrane disruption, membrane potential, and leakage of cellular components. Additionally, 1 and 2 showed a synergistic effect with commercially available antibiotics such as vancomycin with enhanced antibacterial activity. However, 1 possesses higher antibacterial, antibiofilm, and antivirulence actions, making it a potent therapeutic agent against both MRSA BAA1717 and MRSA CI1 strains.