Re nanoflower-decorated carbon cloth for pH-universal hydrogen evolution reaction: Unveiling the intrinsic electrocatalytic activity of metallic Re.

[Display omitted] • Electrocatalytic Re nanoflowers (Re NFs) were grown on a carbon cloth (CC) substrate. • Optimal synthesis and growth mechanism of Re NFs on CC were validated. • Density functional theory (DFT) calculations determined intrinsic HER activity of Re. • Hydrogen evolution reaction (HER) activity of Re in different pH environments was evaluated. • ReNF@CC performed eminent HER activities with significantly reduced overpotentials. The hydrogen evolution reaction (HER) is one of the primary routes for clean hydrogen energy production to replace fossil fuels. However, the lack of cost-effective electrocatalysts hinders its practical implementation. Re, which is considerably less expensive than Pt, has recently emerged as an electrocatalyst owing to its high HER activity over a wide pH range. However, HER processes of Re have been studied primarily through spectroscopy, with little theoretical interpretation to explain the intrinsic HER activity of Re. Additionally, it is necessary to develop antioxidative Re electrocatalysts to prevent hydrogen intercalation, and to suppress catalyst aggregation to ensure long-term stability. In this work, a theoretical analysis was first conducted to investigate the free energy of each HER intermediate and demonstrate high performance of Re. Then, a novel free-standing electrocatalyst consisting of Re nanoflowers (NFs) grown in-situ on a carbon cloth (CC) was synthesized (ReNF@CC) via a hydrothermal method followed by thermal annealing. The Re NFs homogeneously grown on the CC surface effectively suppressed self-aggregation to preserve abundant active sites, and the direct coupling of Re NFs enhanced the conductivity and physical/electrochemical stability to prevent their detachment from the CC during operation. A high HER performance was obtained with low overpotentials of 103, 115, and 75 mV at 10 mA cm−2 in 0.5 M H 2 SO 4 , 1 M PBS, and 1 M KOH, respectively; additionally, a superior durability with respect to commercial Pt/C was achieved. Overall, this study offers a versatile and universal strategy for highly efficient water electrolysis in different media. [ABSTRACT FROM AUTHOR]