Sr-induced Fermi Engineering of ß-FeOOH for Multifunctional Catalysis.

Designing a multifunctional electrocatalyst to produce H2 from water, urea, urine, and wastewater, is highly desirable yet challenging because it demands precise Fermi-engineering to realize stronger π-donation from O 2p to electron(e- )-deficient metal (t2g ) d-orbitals. Here a Sr-induced phase transformed ß-FeOOH/α-Ni(OH)2 catalyst anchored on Ni-foam (designated as pt-NFS) is introduced, where Sr produces plenteous Fe4+ (Fe3+ → Fe4+ ) to modulate Fermi level and e- -transfer from e- -rich Ni3+ (t2g )-orbitals to e- -deficient Fe4+ (t2g )-orbitals, via strong π-donation from the π-symmetry lone-pair of O bridge. pt-NFS utilizes Fe-sites near the Sr-atom to break the H─O─H bonds and weakens the adsorption of *O while strengthening that of *OOH, toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Invaluably, Fe-sites of pt-NFS activate H2 -production from urea oxidation reaction (UOR) through a one-stage pathway which, unlike conventional two-stage pathways with two NH3 -molecules, involves only one NH3 -molecule. Owing to more suitable kinetic energetics, pt-NFS requires 133 mV (negative potential shift), 193 mV, ≈1.352 V, and ≈1.375 V versus RHE for HER, OER, UOR, and human urine oxidation, respectively, to reach the benchmark 10 mA cm-2 and also demonstrates remarkable durability of over 25 h. This work opens a new corridor to design multifunctional electrocatalysts with precise Fermi engineering through d-band modulation.

Electron-Sponge Nature of Polyoxometalates for Next-Generation Electrocatalytic Water Splitting and Nonvolatile Neuromorphic Devices.

Designing next-generation molecular devices typically necessitates plentiful oxygen-bearing sites to facilitate multiple-electron transfers. However, the theoretical limits of existing materials for energy conversion and information storage devices make it inevitable to hunt for new competitors. Polyoxometalates (POMs), a unique class of metal-oxide clusters, have been investigated exponentially due to their structural diversity and tunable redox properties. POMs behave as electron-sponges owing to their intrinsic ability of reversible uptake-release of multiple electrons. In this review, numerous POM-frameworks together with desired features of a contender material and inherited properties of POMs are systematically discussed to demonstrate how and why the electron-sponge-like nature of POMs is beneficial to design next-generation water oxidation/reduction electrocatalysts, and neuromorphic nonvolatile resistance-switching random-access memory devices. The aim is to converge the attention of scientists who are working separately on electrocatalysts and memory devices, on a point that, although the application types are different, they all hunt for a material that could exhibit electron-sponge-like feature to realize boosted performances and thus, encouraging the scientists of two completely different fields to explore POMs as imperious contenders to design next-generation nanodevices. Finally, challenges and promising prospects in this research field are also highlighted.