RESUMEN
Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.
RESUMEN
Integrating the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) is an energy-saving approach for electrolytic H2 production. Here, hollow NiCoP nanoprisms are derived from Prussian blue analogues by a combined self-template coordination reaction and gas-phase phosphorization strategy. Benefiting from the strong electron interaction, unique hollow nanostructure, and enhanced mass/charge transfer, NiCoP nanoprisms display outstanding alkaline HER and UOR performance. Specifically, low potentials of -0.052, -0.115, and -0.159 V for HER and ultralow potentials of 1.30, 1.36, and 1.42 V for UOR at current densities of 10, 50, and 100 mA cm-2 are obtained. Moreover, in a urea-assisted water electrolysis system, NiCoP nanoprisms only require cell voltages of 1.36, 1.49, and 1.57 V to offer current densities of 10, 50, and 100 mA cm-2 , about 170, 180, and 200 mV less than the traditional water electrolysis. Theoretical calculations indicate the Co substitution in Ni2 P promotes the adsorption and dissociation of water molecules, optimizes the desorption energy of active hydrogen atoms, and enhances the adsorption of urea molecules, thus accelerating the kinetics of HER and UOR. This work facilitates the application of hollow bimetallic phosphides in electrochemical preparation of clean energy and provides a successful paradigm for urea-rich wastewater electrolysis.
RESUMEN
In this article, a new zinc-containing ionic liquid (IL) [HMMIm]2[ZnCl4] (HMMIm = 1-hexyl-2,3-dimethyl-imidazolium) is designed, which acts as a multifunctional source for the interfacial engineering of ZnS nanodots (NDs). Given the electrostatic interaction driven by the imidazolium cation, the steric effect of the alkyl chain, and the in situ released Zn ion from the IL, [HMMIm]2[ZnCl4] shows great advantages in controlling the formation of ZnS NDs. Based on this strategy, a nanocomposite consisting of homodispersed ZnS NDs anchored on sulfur/nitrogen dual-doped reduced graphene oxide (ZnS-NDs@SNG) is prepared. When evaluated as an anode material for lithium-ion batteries (LIBs), the nanocomposite delivers high reversible specific capacity, excellent high-rate performance, and superior cycling life. In particular, a discharge capacity of 648.1 mA h g-1 can be achieved at a high current density (10.0 A g-1) over 5000 cycles. Benefitting from the multifunctional IL and the simple synthesis protocol, the IL-assisted interfacial engineering strategy will enable a new avenue for the controllable synthesis of metal-sulfide-based anode materials.
