Rapid Synthesis of Ruthenium-Copper Nanocomposites as High-Performance Bifunctional Electrocatalysts for Electrochemical Water Splitting.

Development of high-performance, low-cost catalysts for electrochemical water splitting is key to sustainable hydrogen production. Herein, ultrafast synthesis of carbon-supported ruthenium-copper (RuCu/C) nanocomposites is reported by magnetic induction heating, where the rapid Joule's heating of RuCl3 and CuCl2 at 200 A for 10 s produces Ru-Cl residues-decorated Ru nanocrystals dispersed on a CuClx scaffold, featuring effective Ru to Cu charge transfer. Among the series, the RuCu/C-3 sample exhibits the best activity in 1 m KOH toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with an overpotential of only -23 and +270 mV to reach 10 mA cm-2, respectively. When RuCu/C-3 is used as bifunctional catalysts for electrochemical water splitting, a low cell voltage of 1.53 V is needed to produce 10 mA cm-2, markedly better than that with a mixture of commercial Pt/C+RuO2 (1.59 V). In situ X-ray absorption spectroscopy measurements show that the bifunctional activity is due to reduction of the Ru-Cl residues at low electrode potentials that enriches metallic Ru and oxidation at high electrode potentials that facilitates the formation of amorphous RuOx. These findings highlight the unique potential of MIH in the ultrafast synthesis of high-performance catalysts for electrochemical water splitting.

Stabilization and Surface Functionalization of Palladium Disulfide Nanoparticles with Acetylene Derivatives.

Metal chalcogenide nanoparticles have been attracting extensive attention in diverse fields. Traditionally these nanoparticles are stabilized by organic ligands such as thiols and amines involving nonconjugated core-ligand interfacial interactions. In the present study, a facile wet-chemistry method is described for the synthesis of palladium disulfide (PdS2) nanoparticles capped with acetylene derivatives. Spectroscopic and electrochemical measurements suggest that conjugated Pd-C≡ linkages are formed at the core-ligand interface and facilitate electronic coupling and hence manipulation of the nanoparticle optical and electronic properties. The unique interfacial linkages also allow further functionalization of the nanoparticles by metathesis reaction with olefin derivatives, as manifested in the reaction with vinylferrocene. This research opens new avenues for the structural engineering and functionalization of metal chalcogenide nanoparticles.

Alkyne-Functionalized Platinum Chalcogenide (S, Se) Nanoparticles.

Metal chalcogenide nanoparticles play a vital role in a wide range of applications and are typically stabilized by organic derivatives containing thiol, amine, or carboxyl moieties, where the nonconjugated particle-ligand interfaces limit the electronic interactions between the inorganic cores and organic ligands. Herein, a wet-chemistry method is developed for the facile preparation of stable platinum chalcogenide (S, Se) nanoparticles capped with acetylene derivatives (e.g., 4-ethylphenylacetylene, EPA). The formation of Pt-C≡ conjugated bonds at the nanoparticle interfaces, which is confirmed by optical and X-ray spectroscopic measurements, leads to markedly enhanced electronic interactions between the d electrons of the nanoparticle cores and π electrons of the acetylene moiety, in stark contrast to the mercapto-capped counterparts with only nonconjugated Pt-S- interfacial bonds, as manifested in spectroscopic measurements and density functional theory calculations. This study underscores the significance of conjugated anchoring linkages in the stabilization and functionalization of metal chalcogenides, a unique strategy for diverse applications.

Nanozymes for the Therapeutic Treatment of Diabetic Foot Ulcers.

Diabetic foot ulcers (DFU) are chronic, refractory wounds caused by diabetic neuropathy, vascular disease, and bacterial infection, and have become one of the most serious and persistent complications of diabetes mellitus because of their high incidence and difficulty in healing. Its malignancy results from a complex microenvironment that includes a series of unfriendly physiological states secondary to hyperglycemia, such as recurrent infections, excessive oxidative stress, persistent inflammation, and ischemia and hypoxia. However, current common clinical treatments, such as antibiotic therapy, insulin therapy, surgical debridement, and conventional wound dressings all have drawbacks, and suboptimal outcomes exacerbate the financial and physical burdens of diabetic patients. Therefore, development of new, effective and affordable treatments for DFU represents a top priority to improve the quality of life of diabetic patients. In recent years, nanozymes-based diabetic wound therapy systems have been attracting extensive interest by integrating the unique advantages of nanomaterials and natural enzymes. Compared with natural enzymes, nanozymes possess more stable catalytic activity, lower production cost and greater maneuverability. Remarkably, many nanozymes possess multienzyme activities that can cascade multiple enzyme-catalyzed reactions simultaneously throughout the recovery process of DFU. Additionally, their favorable photothermal-acoustic properties can be exploited for further enhancement of the therapeutic effects. In this review we first describe the characteristic pathological microenvironment of DFU, then discuss the therapeutic mechanisms and applications of nanozymes in DFU healing, and finally, highlight the challenges and perspectives of nanozyme development for DFU treatment.

Photocatalytic Generation of Singlet Oxygen by Graphitic Carbon Nitride for Antibacterial Applications.

Carbon-based functional nanocomposites have emerged as potent antimicrobial agents and can be exploited as a viable option to overcome antibiotic resistance of bacterial strains. In the present study, graphitic carbon nitride nanosheets are prepared by controlled calcination of urea. Spectroscopic measurements show that the nanosheets consist of abundant carbonyl groups and exhibit apparent photocatalytic activity under UV photoirradiation towards the selective production of singlet oxygen. Therefore, the nanosheets can effectively damage the bacterial cell membranes and inhibit the growth of bacterial cells, such as Gram-negative Escherichia coli, as confirmed in photodynamic, fluorescence microscopy, and scanning electron microscopy measurements. The results from this research highlight the unique potential of carbon nitride derivatives as potent antimicrobial agents.

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization.

Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet-chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet-like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand-core interface in the former, in contrast to mostly non-conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene-capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto-capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.