Nickel‐iron layered double hydroxides (Ni‐Fe LDHs) consist of stacked Fe3+‐doped positively charged Ni‐hydroxide layers containing charge‐balancing anions and water molecules between the layers. Although Ni‐Fe LDHs are highly active in the oxygen evolution reaction (OER) under alkaline conditions, their poor operational stability remains an issue. Herein, based on density functional theory calculations, it is proposed that the inclusion of a higher Fe content (>40%) than the theoretical Fe3+ limit (≈25%) permitted by Ni‐Fe LDHs can lead to improved structural stability. An Fe‐rich Ni‐Fe LDH electrode is therefore prepared via a growth strategy based on the controlled oxygen corrosion of an Fe substrate, by enabling the incorporation of additional Fe2+ into the Ni2+‐Fe3+ LDH structure. Indeed, microstructural and elemental analysis confirm the presence of additional Fe2+. This Fe‐rich Ni‐Fe LDH electrode not only offers a low OER overpotential (≈270 mV at 200 mA cm−2) but also exhibits an excellent operational stability under dynamic operating environments without any significant performance degradation or metal ion dissolution. Finally, the practical feasibility of the Fe‐rich Ni‐Fe LDH electrode is demonstrated in a single‐cell (34.56 cm2) operation. These findings are expected to aid in the development of reliable OER electrodes for use in commercial water electrolyzers.

Securing the electrochemical durability of noble metal platinum is of central importance for the successful implementation of a proton exchange membrane fuel cell (PEMFC). Pt dissolution, a major cause of PEMFC degradation, is known to be a potential-dependent transient process, but its underlying mechanism is puzzling. Herein, we elucidate a chemical Pt dissolution process that can occur in various electrocatalytic conditions. This process intensively occurs during potential perturbations with a millisecond timescale, which has yet to be seriously considered. The open circuit potential profiles identify the dominant formation of metastable Pt species at such short timescales and their simultaneous dissolution. Considering on these findings, a proof-of-concept strategy for alleviating chemical Pt dissolution is further studied by tuning electric double layer charging. These results suggest that stable Pt electrocatalysis can be achieved if rational synthetic or systematic strategies are further developed.

Platinum single-atom catalysts (SACs) hold promise as a new frontier in heterogeneous electrocatalysis. However, the exact chemical nature of active Pt sites is highly elusive, arousing many hypotheses to compensate for the significant discrepancies between experiments and theories. Here, we identify the stabilization of low-coordinated PtII species on carbon-based Pt SACs, which have rarely been found as reaction intermediates of homogeneous PtII catalysts, but have often been proposed as catalytic sites for Pt SACs from theory. Advanced online spectroscopic studies reveal multiple identities of PtII moieties on the SACs beyond ideally four-coordinated PtII–N4. Notably, decreasing Pt content to 0.15 wt.% enables the differentiation of low-coordinated PtII species from the four-coordinated ones, demonstrating their critical role in the chlorine evolution reaction (CER). This study suggests general guidelines for achieving high electrocatalytic performance of carbon-based SACs based on all other d8 metal ions, e.g., NiII and PdII as well as PtII.

The catalytic redox activity of Cu(II) bound to the amino-terminal copper and nickel (ATCUN) binding motif (Xxx-Zzz-His, XZH) is stimulating the development of catalytic metallodrugs based on reactive oxygen species (ROS)-mediated biomolecule oxidation. However, low Cu(I) availability resulting from the strong Cu(II) binding affinity of the ATCUN motif is regarded as a limitation to efficient ROS generation. To address this, we replaced the imidazole moiety (pK a 7.0) of Gly−Gly− His−NH 2 (GGHa, a canonical ATCUN peptide) with thiazole (pK a 2.7) and oxazole (pK a 0.8), yielding GGThia and GGOxa, respectively. A newly synthesized amino acid, Fmoc-3-(4oxazolyl)-L-alanine, served as a histidine surrogate featuring an azole ring with the lowest pK a among known analogues. Despite similar square-planar Cu(II)−N 4 geometries being observed for the three Cu(II)−ATCUN complexes by electron paramagnetic resonance spectroscopy and X-ray crystallography, the azole modification enabled the Cu(II)−ATCUN complexes to exhibit significant rate enhancement for ROS-mediated DNA cleavage. Further analyses based on Cu(I)/Cu(II) binding affinities, electrochemical measurements, density functional theory calculations, and X-ray absorption spectroscopy indicated that the azole modification enhanced the accessibility of the Cu(I) oxidation state during ROS generation. Our oxazole/thiazole-containing ATCUN motifs provide a new design strategy for peptide ligands with modulated N donor ability, with potential applications in the development of ROS-mediated metallodrugs.