Electronic structure modulation of catalytic active atoms in the catalyst design is an attractive route for realizing active and stable hydrogen evolution reaction (HER). The role of duet or even...

Finding out the catalysis trend is an important prerequisite for the development of advanced or untouched catalysts. Intermetallic silicides composed of interstitial Si and Pt-group metals (PGMs) are currently rarely reported as hydrogen evolution reaction (HER) catalysts due to the absence of accessibility and predictability. Herein, by theoretical calculations, we unveil the activity trend of PGM silicides and show that IrSi is the most efficient HER catalyst because of the appropriate d-band center and optimal adsorption behavior. Furthermore, we pioneer the use of the molten salt-assisted synthesis strategy to successfully synthesize a series of PGM silicides (IrSi, PtSi, Pd 2 Si, RhSi, and RuSi x ) under normal pressure and mild conditions by overcoming the slow diffusion of silicon (Si) and verify the generality of this strategy. Electrochemical evaluation demonstrates that IrSi indeed possesses excellent HER catalysis activity, outperforming the commercial Pt catalyst, with an ultralow overpotential of 24 mV to achieve 10 mA cm −2 in acidic media, and the predicted activity trend is further fitted experimentally. This work provides a valuable prediction result for catalysis and a feasible general method for construction of PGM silicides.

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.

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.

Correction for ‘Duetting electronic structure modulation of Ru atoms in RuSe2@NC enables more moderate H* adsorption and water dissociation for hydrogen evolution reaction’ by Ding Chen et al., J. Mater. Chem. A, 2022, 10, 7637–7644, https://doi.org/10.1039/d2ta01032a.