▎ 摘　　要

Transition-metal borides belong to a small class of non-noble-metal electrocatalysts that exhibit excellent activity toward the hydrogen evolution reaction (HER) already in bulk form; those containing graphene-like (flat) boron layers, such as alpha-MoB2, are particularly promising. In this study, the first tungsten-based boride HER electrocatalysts were studied experimentally and theoretically. Tungsten, the diborides of which (alpha- and beta-WB2) contain both the active graphene-like (flat) boron layer and the less active phosphorene-like (puckered) boron layer, could be successfully substituted (up to 30 at %) for molybdenum in alpha-MoB2. The resulting alpha-Mo1-xWxB2 exhibited better HER activity and stability than the binaries WB2 and MoB2, especially at high current density in acidic electrolytes. DFT calculations showed that the graphene-like boron layer is the most active among the studied surfaces and that tungsten promotes hydrogen generation by facilitating bonding between hydrogen atoms in contrast to molybdenum. These results should pave the way for high-current-density, abundant, and inexpensive bulk and nanoscale HER catalysts by applying structure-activity relationships.