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Synthesis of catalysts with high activity for hydrogen evolution reaction (HER) has been a hot topic in electrocatalysis. In this paper, using MIL-88A(Fe) metal-organic complex, polyoxometalate (POM) and H2PtCl6 as starting materials, hierarchic and low Pt0-loading micro-rods (denoted as Pt-POMFe, i.e. Pt-PW12Fe or Pt-PMo12Fe) have been synthesized, in which the Pt0 nanoparticles can be stabilized by POM. The Pt-PW12Fe micro-rod containing [PW12O40]3- polyoxoanion component (0.30% Pt0-loading) which retains the spindle structure of its parent MIL-88A(Fe) exhibits a low overpotential of 28 mV at current density of 10 mA·cm−2 for HER that is close to the electrocatalytic effect of commercial Pt/C (ca. 20% Pt0-loading). Such high electrocatalytic reactivity is mainly caused by the synergistic effect of the three components of POM, Pt0, and Fe3O4@C. The structure effectively increases the active sites of the catalyst and improves its conductivity and stability. The Pt-POMFe catalyst extends a new family of MOF-POM functional materials and provides a new concept to the design and synthesis of highly-efficient and low-cost electrocatalyst for hydrogen production. [ABSTRACT FROM AUTHOR]

Developing cost‐effective and highly active hydrogen evolution reaction (HER) electrocatalysts is of pivotal importance in the roadmap of hydrogen economy. Increasing active sites and improving conductivity are two effective strategies to optimize the performance of electrocatalyst. In this paper, we report a highly active HER catalyst consisting of ultra‐small molybdenum carbide nanoparticles uniformly entrapped in mesoporous carbon microspheres (Mo2C@MCS) fabricated by in situ synthesis. In 1 M KOH, the catalyst exhibits an excellent HER performance with a pretty low overpotential (134 mV at current density of 10 mA cm−2) and a small Tafel slope (51 mV dec−1), which exceeded the currently reported un‐doped Mo2C catalyst. The excellent HER performance is attributed to the abundant active sites provided by the ultra‐small Mo2C nanoparticles as well as the superior conductivity originated from carbon matrix and the intimate contact between Mo2C nanoparticles and mesoporous carbon wall. [ABSTRACT FROM AUTHOR]