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Molybdenum carbides (MoxC) have shown high catalytic activities toward hydrogen evolution reaction (HER) when coupled with graphene. Herein, we use density functional theory (DFT) calculations in conjunction with ab initio thermodynamics and electrochemical modeling on γ-MoC supported graphene to determine the origin of the enhanced HER activities. In addition to previous claims that graphene's main role is to prevent agglomeration of MoxC nanoparticles, we show that the interplay between γ-MoC coupling and graphene defect chemistry ac