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(d_(M-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(d_(Os-Os))gradually increases from 2.73 to 2.96?.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 H_2O 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?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.

Tunable Ru-Ru2P heterostructures with charge redistribution for efficient pH-universal hydrogen evolution

Designing synergistic heterogeneous catalytic interfaces is the key to developing highly compatible pH-universal electrocatalysts for complex chemical environments.Our theoretical calculation results demonstrate that the Ru-Ru2P heterointerface can not only promote the redistribution of charges,but also reduce the d-band center,and then enhances the adsorption capacity of the key intermediate.However,in situ and facile synthesis of Ru-Ru2P heterostructures is severely limited by thermodynamic obstacles.Herein,we propose a molten salt-assisted catalytic synthesis scheme,and successfully build a series of homologous metallic Ru-Ru2P heterostructure catalysts with different molar ratios of Ru to P under atmospheric pressure and low-temperature(400C).The resultant Ru-Ru2P with rich heterostructures show the Pt-like HER performance in different pH media.Particularly,it is prominent under alkaline conditions(18 mV@10 mA cm^(2)),which outperforms the Pt catalyst(37 mV@10 mA cm^(2)).Furthermore,Ru-Ru2P heterostructures also show certain potential in the electrolysis of seawater to produce hydrogen.This work represents a significant supplement of high-efficiency pH-universal HER catalysts,and provides a new light on interface engineering in energy technology fields and beyond.