Highly Active and Robust Catalyst: Co2B-Fe2B Heterostructural Nanosheets with Abundant Defects for Hydrogen Production.

A high-performance and reusable nonnoble metal catalyst for catalyzing sodium borohydride (NaBH4) hydrolysis to generate H2 is heralded as a nuclear material for the fast-growing hydrogen economy. Boron vacancy serves as a flexible defect site that can effectively regulate the catalytic hydrolysis performance. Herein, we construct a uniformly dispersed and boron vacancy-rich nonnoble metal Co2B-Fe2B catalyst via the hard template method. The optimized Co2B-Fe2B exhibits superior performance toward NaBH4 hydrolysis, with a high hydrogen generation rate (5315.8 mL min-1 gcatalyst-1), relatively low activation energy (35.4 kJ mol-1), and remarkable cycling stability, outperforming the majority of reported catalysts. Studies have shown that electron transfer from Fe2B to Co2B, as well as abundant boron defects, can effectively modulate the charge carrier concentration of Co2B-Fe2B catalysts. Density functional theory calculations confirm that the outer electron cloud density of Co2B is higher than that of Fe2B, among which Co2B with high electron cloud density can selectively adsorb BH4- ions, while the electron-deficient Fe2B is favorable for capturing H2O molecules, therefore synergistically promoting the catalytic NaBH4 hydrolysis to produce H2.

Synergistic Regulation of Pt Clusters on Porous Support by Mo and P for Robust Bifunctional Hydrogen Electrocatalysis.

Developing efficient electrocatalysts toward hydrogen oxidation and evolution reactions (HER/HOR) in alkaline electrolytes is essential for realizing renewable hydrogen technologies. Herein, we demonstrate that the introduction of dual-active species such as Mo and P (Pt/Mo,P@NC) can effectively regulate the surface electronic structure of platinum (Pt) and significantly improve the HOR/HER performance. The optimized Pt/Mo,P@NC exhibits remarkable catalytic activity, achieving a normalized exchange current density of 2.89 mA cm-2 and a mass activity of 2.3 mA µgPt-1, which are approximately 2.2 and 13.5 times higher than those of the state-of-the-art Pt/C catalyst, respectively. Moreover, it performs an impressive HER performance with an overpotential of 23.4 mV at 10 mA cm-2, which is lower than most documented alkaline electrocatalysts. Experimental results reveal that the modifying effect of Mo and P optimizes the adsorption of H and OH on Pt/Mo,P@NC, resulting in an outstanding catalytic performance. This work has significant theoretical and practical significance for developing a novel and highly efficient catalyst for bifunctional hydrogen electrocatalysis.

Electronic Modulation and Mechanistic Study of Ru-Decorated Porous Cu-Rich Cuprous Oxide for Robust Alkaline Hydrogen Oxidation and Evolution Reactions.

Rational design of high-efficiency and viable electrocatalysts is essential in overcoming the bottleneck of sluggish alkaline hydrogen oxidation/evolution reaction (HOR/HER) kinetics. In this study, a metal-organic framework-derived strategy for constructing a Pt-free catalyst with Ru clusters anchored on porous Cu-Cu2 O@C is proposed. The designed Ru/Cu-Cu2 O@C exhibits superior HOR performance, with a mass activity of 2.7 mA µ g R u - 1 ${{{\rm \mu }{\rm g}}_{{\rm R}{\rm u}}^{-1}}$ at 50 mV, which is about 24 times higher than that of state-of-the-art Pt/C (0.11 mA µ g P t - 1 ${{{\rm \mu }{\rm g}}_{{\rm P}{\rm t}}^{-1}}$ ). Significantly, Ru/Cu-Cu2 O@C also displays impressive HER performance by generating 26 mV at 10 mA cm-2 , which exceeds the majority of documented Ru-based electrocatalysts. Systematic characterization and density functional theory (DFT) calculations reveal that efficient electron transfer between Ru and Cu species results in an attenuated hydrogen binding energy (HBE) of Ru and an enhanced hydroxy binding energy (OHBE) of Cu2 O, together with an optimized H2 O adsorption energy with Cu2 O as the H2 O*-capturing site, which jointly facilitates HOR and HER kinetics.