ABSTRACT
Electrochemical CO2 reduction reaction (CO2 RR) is a promising strategy for waste CO2 utilization and intermittent electricity storage. Herein, it is reported that bimetallic Cu/Pd catalysts with enhanced *CO affinity show a promoted CO2 RR performance for multi-carbon (C2+) production under industry-relevant high current density. Especially, bimetallic Cu/Pd-1% catalyst shows an outstanding CO2 -to-C2+ conversion with 66.2% in Faradaic efficiency (FE) and 463.2 mA cm-2 in partial current density. An increment in the FE ratios of C2+ products to CO for Cu/Pd-1% catalyst further illuminates a preferable C2+ production. In situ Raman spectra reveal that the atop-bounded CO is dominated by low-frequency band CO on Cu/Pd-1% that leads to C2+ products on bimetallic catalysts, in contrast to the majority of high-frequency band CO on Cu that favors the formation of CO. Density function theory calculation confirms that bimetallic Cu/Pd catalyst enhances the *CO adsorption and reduces the Gibbs free energy of the CC coupling process, thereby favoring the formation of C2+ products.
ABSTRACT
Noble metal electrocatalysts (e.g., Pt, Ru, etc.) suffer from sluggish kinetics of water dissociation for the electrochemical reduction of water to molecular hydrogen in alkaline and neutral pH environments. Herein, we found that an integration of Ru nanoparticles (NPs) on oxygen-deficient WO3-x manifested a 24.0-fold increase in hydrogen evolution reaction (HER) activity compared with commercial Ru/C electrocatalyst in neutral electrolyte. Oxygen-deficient WO3-x is shown to possess large capacity for storing protons, which could be transferred to the Ru NPs under cathodic potential. This significantly increases the hydrogen coverage on the surface of Ru NPs in HER and thus changes the rate-determining step of HER on Ru from water dissociation to hydrogen recombination.
ABSTRACT
Recently, extensive research efforts have been devoted to drive electrocatalytic water-splitting for hydrogen generation by electricity or solar cells. However, electricity from power grid and the intermittent property of sunlight inevitably brings about environmental pollution and energy loss. Thus, a novelty energy system for simultaneous generating H2 from solar energy and overcoming the intermittence of sunlight is highly desirable. Herein, a self-powered energy system with solar energy as the sole input energy is successfully assembled by integrated Zn-air batteries with stable output voltage, solar cells, and water splitting electrolyzer to efficient H2 production. Specially, the Zn-air batteries are charged by the solar cell to store intermitted solar energy as electricity during light reaction. Under unassisted light reaction, the batteries could release electric energy to drive H2 production. Therefore, the aim for simultaneous generating H2 and eliminating the restrictions of intermittent sunlight are realized. The solar-to-hydrogen efficiency and solar-to-water splitting device efficiency of the self-powered energy system are up to 4.6% and 5.9%, respectively. This work provides the novel design systems for H2 production and the usage of renewable energy.
ABSTRACT
Constructing strong oxide-support interaction (SOSI) is compelling for modulating the atomic configurations and electronic structures of supported catalysts. Herein, ultrafine iridium oxide nanoclusters (≈1 nm) are anchored on vanadium oxide support (IrO2 /V2 O5 ) via SOSI. The as made catalyst, with a unique distorted IrO2 structure, is discovered to significantly boost the performance for pH-universal oxygen evolution reaction (OER). Based on experimental results and theoretical calculations, the distorted IrO2 active sites with flexible redox states in IrO2 /V2 O5 server as electrophilic centers balance the adsorption of oxo-intermediates and effectively facilitate the process of OO coupling, eventually propelling the fast turnover of water oxidation. As a result, IrO2 /V2 O5 demonstrates not only ultralow overpotentials at 10 mA cm-2 (266 mV, pH = 0; 329 mV, pH = 7; 283 mV, pH = 14) for OER, but also high-performance overall water electrolysis over a broad pH range, with a potential of mere 1.50 V (pH = 0), 1.65 V (pH = 7) or 1.49 V (pH = 14) at 10 mA cm-2 . In addition, SOSI can simultaneously secure the distorted active sites and thus remarkably improving the catalytic stability, making it a promising strategy to develop high-performance catalytic systems.
