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.

Hierarchical V4C3TX@NiO-reduced graphene oxide heterostructure hydrogels and defective reduced graphene oxide hydrogels as free-standing anodes and cathodes for high-performance asymmetric supercapacitors.

Asymmetric supercapacitors (ASCs) based on a battery-type anode and a capacitive-type cathode have been attracting extensive interest because of their high energy density. Herein, NiO nanosheets are hydrothermally deposited onto a V4C3TX substrate, which are then assembled into a 3D porous heterostructure hydrogel through a graphene oxide-assisted self-convergence hydrothermal process at low temperatures. The resultant hierarchical V4C3TX@NiO-RGO heterostructure hydrogel exhibits an ultrahigh specific capacitance of up to 1014.5 F g-1 at 1 A g-1. In addition, a defective reduced graphene oxide (DRGO) hydrogel is prepared using a cost-effective hydrothermal procedure followed by cobalt-catalyzed gasification, which shows a higher specific capacitance (258 F g-1 at 1 A g-1) than the untreated RGO hydrogel (176 F g-1). These two electrodes are then assembled into an ASC; the device features a stable operating voltage of 1.8 V, a maximum energy density of 86.22 W h kg-1 at 900 W kg-1, and excellent cycling stability at 96.4% capacitance retention after 10 000 cycles at 10 A g-1. The results from this work highlight the unique potential of MXene-based materials for the construction of high-performance ASCs.

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction.

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. This is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

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.

Hydrophobic, flexible electromagnetic interference shielding films derived from hydrolysate of waste leather scraps.

With the rapid development of wireless telecommunication technologies, it is of fundamental and technological significance to design and engineer high-performance shielding materials against electromagnetic interference (EMI). Herein, a three-step procedure is developed to produce hydrophobic, flexible nanofiber films for EMI shielding and pressure sensing based on hydrolysate of waste leather scraps (HWLS): (i) electrospinning preparation of HWLS/polyacrylonitrile (PAN) nanofiber films, (ii) adsorption of silver nanowires (AgNWs) onto HWLS/PAN nanofiber films, and (iii) coating of HWLS/PAN/AgNWs nanofiber films with polydimethylsiloxane (PDMS). Scanning electron microscopy studies show that AgNWs are interweaved with HWLS/PAN nanofibers to form a conductive network, exhibiting an electrical conductivity of 105 S m-1 and shielding efficiency of 65 dB for a 150 µm-thick HWLS/PAN/AgNWs film. The HWLS/PAN/AgNWs/PDMS film displays an even better electromagnetic shielding efficiency of 80 dB and a water contact angle of 132.5°. Results from this study highlight the unique potential of leather solid wastes for the production of high-performance, environmentally friendly, and low-cost EMI shielding materials.