ABSTRACT
Applications of zinc-air batteries are partially limited by the slow kinetics of oxygen reduction reaction (ORR); Thus, developing effective strategies to address the compatibility issue between performance and stability is crucial, yet it remains a significant challenge. Here, we propose an in situ gas etching-thermal assembly strategy with an in situ-grown graphene-like shell that will favor Mn anchoring. Gas etching allows for the simultaneous creation of mesopore-dominated carbon cores and ultrathin carbon layer shells adorned entirely with highly dispersed Mn-N4 single-atom sites. This approach effectively resolves the compatibility issue between activity and stability in a single step. The unique core-shell structure allows for the full exposure of active sites and effectively prevents the agglomerations and dissolution of Mn-N4 sites in cores. The corresponding half-wave potential for ORR is up to 0.875 V (vs. reversible hydrogen electrode (RHE)) in 0.1 M KOH. The gained catalyst (Mn-N@Gra-L)-assembled zinc-air battery has a high peak power density (242 mW cm-2) and a durability of â¼ 115 h. Furthermore, replacing the zinc anode achieved a stable cyclic discharge platform of â¼ 20 h at varying current densities. Forming more fully exposed and stable existing Mn-N4 sites is a governing factor for improving the electrocatalytic ORR activity, significantly cycling durability, and reversibility of zinc-air batteries.
ABSTRACT
The development of cerium (Ce) single-atom (SA) electrocatalysts for oxygen reduction reaction (ORR) with high active-site utilization and intrinsic activity has become popular recently but remains challenging. Inspired by an interesting phenomenon that pore-coupling with single-metal cerium sites can accelerate the electron transfer predicted by density functional theory calculations, here, a facile strategy is reported for directional design of a highly active and stable Ce SA catalyst (Ce SA/MC) by the coupling of single-metal Ce-N4 sites and mesopores in nanocarbon via pore-confinement-pyrolysis of Ce/phenanthroline complexes combined with controlling the formation of Ce oxides. This catalyst delivers a comparable ORR catalytic activity with a half-wave potential of 0.845 V versus RHE to the Pt/C catalyst. Also, a Ce SA/MC-based zinc-air battery (ZAB) has exhibited a higher energy density (924 Wh kgZn -1 ) and better long-term cycling durability than a Pt/C-based ZAB. This proposed strategy may open a door for designing efficient rare-earth metal catalysts with single-metal sites coupling with porous structures for next-generation energy devices.
ABSTRACT
The poor oxygen diffusion and sluggish oxygen reduction reaction (ORR) kinetics at multiphase interfaces in the cathode suppress the practical application of zinc-air batteries. Developing effective strategies to tackle the issue is of great significance for overcoming the performance bottleneck but remains challenging. Here, a multiscale hydrophobic surface is designed on the iron single-atom catalyst via a gas-phase fluorination-assisted method inspired by the structure of gas-trapping mastoids on lotus leaves. The hydrophobic Fe-FNC attains a higher peak power density of up to 226 mW cm-2 , a long durability of up close to 140 h, and better cyclic durability of up to 300 cycles compared to the corresponding Pt/C-based Zn-air battery. Experiments and theoretical calculations indicate that the formed more triple-phase interfaces and exposed isolated Fe-N4 sites are proposed as the governing factors in boosting electrocatalytic ORR activity and remarkable cycling durability for Zn-air batteries.
ABSTRACT
Developing catalysts with superior activity to hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is equally important to the overall photoelectrochemical water splitting to produce hydrogen. In this work, bismuth oxyiodide (BiOI), iron-modified bismuth iodide Fe/BiOI, and the sulfurized S-Fe/BiOI were prepared using the solvothermal method. The three materials all have good absorption ability for visible light. The photoelectrochemical catalytic activity of BiOI to oxygen evolution reaction (OER) is significantly enhanced after iron modification, while the sulfurized product S-Fe/BiOI exhibits better catalytic activity to hydrogen evolution reaction (HER). Hence, OER and HER can be simultaneously catalyzed by using Fe/BiOI and S-Fe/BiOI as anodic and cathodic catalysts to facilitate the overall photoelectrochemical water splitting process.
