Fe-Regulated Amorphous-Crystal Ni(Fe)P2 Nanosheets Coupled with Ru Powerfully Drive Seawater Splitting at Large Current Density.

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.

Work-function-induced Interfacial Built-in Electric Fields in Os-OsSe2 Heterostructures for Active Acidic and Alkaline Hydrogen Evolution.

Theoretical calculations unveil that the formation of Os-OsSe2 heterostructures with neutralized work function (WF) perfectly balances the electronic state between strong (Os) and weak (OsSe2 ) adsorbents and bidirectionally optimizes the hydrogen evolution reaction (HER) activity of Os sites, significantly reducing thermodynamic energy barrier and accelerating kinetics process. Then, heterostructural Os-OsSe2 is constructed for the first time by a molten salt method and confirmed by in-depth structural characterization. Impressively, due to highly active sites endowed by the charge balance effect, Os-OsSe2 exhibits ultra-low overpotentials for HER in both acidic (26 mV @ 10 mA cm-2 ) and alkaline (23 mV @ 10 mA cm-2 ) media, surpassing commercial Pt catalysts. Moreover, the solar-to-hydrogen device assembled with Os-OsSe2 further highlights its potential application prospects. Profoundly, this special heterostructure provides a new model for rational selection of heterocomponents.

Ultralow Ru Incorporated Amorphous Cobalt-Based Oxides for High-Current-Density Overall Water Splitting in Alkaline and Seawater Media.

Realizing efficiency and stable hydrogen production by water electrolysis under high current densities is essential to the forthcoming hydrogen economy. However, its industrial breakthrough is seriously limited by bifunctional catalysts with slow hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalytic processes. Herein, an ultralow Ru incorporated amorphous cobalt-based oxide (Ru-CoOx /NF), effectively driving the electrolysis of water at high current densities in alkaline water and seawater, is designed and constructed. In 1 m KOH, to reach the current density of 1000 mA cm-2 for HER and OER, it only needs 252 and 370 mV overpotentials, respectively, beyond commercial Pt/C and RuO2 catalysts. At the high current density, it also presents outstanding electrochemical stability. Then the electrolyzer apparatus assembled with Ru-CoOx /NF, just requires the ultra-low voltage of 2.2 and 2.62 V to support the current density of 1000 mA cm-2 in alkaline water and seawater electrolysis, respectively, for hydrogen production, better than that of the commercial Pt/C and RuO2 catalysts. This work demonstrates that Ru-CoOx /NF is one of the most promising catalysts for industrial applications and provides a possibility for exploration of high-current-density water electrocatalysis by changing the crystallinity of the catalyst.

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis.

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.