RESUMO
Improving activity and stability of Ruthenium (Ru)-based catalysts in acidic environments is eager to replace more expensive Iridium (Ir)-based materials as practical anode catalyst for proton-exchange membrane water electrolyzers (PEMWEs). Here, a bicontinuous nanoreactor composed of multiscale defective RuO2 nanomonomers (MD-RuO2-BN) is conceived and confirmed by three-dimensional tomograph reconstruction technology. The unique bicontinuous nanoreactor structure provides abundant active sites and rapid mass transfer capability through a cavity confinement effect. Besides, existing vacancies and grain boundaries endow MD-RuO2-BN with generous low-coordination Ru atoms and weakened Ru-O interaction, inhibiting the oxidation of lattice oxygen and dissolution of high-valence Ru. Consequently, in acidic media, the electron- and micro-structure synchronously optimized MD-RuO2-BN achieves hyper water oxidation activity (196 mV @ 10 mA cm-2) and an ultralow degradation rate of 1.2 mV h-1. A homemade PEMWE using MD-RuO2-BN as anode also conveys high water splitting performance (1.64 V @ 1 A cm-2). Theoretical calculations and in-situ Raman spectra further unveil the electronic structure of MD-RuO2-BN and the mechanism of water oxidation processes, rationalizing the enhanced performance by the synergistic effect of multiscale defects and protected active Ru sites.
RESUMO
Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.
RESUMO
Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P2 nanosheet bifunctional catalyst (Ru-Ni(Fe)P2 /NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P2 , and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P2 /NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm-2 for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO2 /NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm-2 and 600 mA cm-2 for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.
