Superhydrophilic molybdenum phosphide quantum dots on porous carbon matrix for boosting hydrogen evolution reaction

• The in-situ confined carbonization of PMo 12 @UiO-66 reduces aggregation and improves conductivity of MoC@PC. • Etching ZrO 2 realizes desired porous MoC@PC with ultra-high specific surface area of 1039 m 2 ·g -1 . • Confined phosphorization of MoC@PC gives raise to superhydrophilic MoP-QDs@PC. • The superhydrophilic MoP-QDs@PC exhibits excellent HER performance superior to commercial 20% Pt/C. Fabricating low-cost, earth-enriched and high-performance electrocatalysts for hydrogen evolution reaction (HER) is significant but challenging for the development of a sustainable hydrogen economy. Herein, we report superhydrophilic molybdenum phosphide quantum dots on porous carbon matrix (MoP-QDs@PC) using polyoxometalates (POMs)-contained metal organic frameworks (MOFs) as precursors, where Keggin-type PMo 12 POMs clusters are confined within the zirconium-based UiO-66 MOFs (denoted as PMo 12 @UiO-66). We demonstrate that the as-formed MoC species by in-situ confined carbonization of PMo 12 @UiO-66 can be converted into superhydrophilic MoP-QDs by further phosphorization, while the porous carbon matrix can be converted into rich P and O co-doped carbon matrix, which greatly increase the wettability and the amount of catalytic active sites exposed to the electrolytes. The as-prepared MoP-QDs@PC electrocatalyst exhibits excellent HER performance, which outperforms commercial 20% Pt/C electrocatalyst when overpotential (η) higher than 197 mV and 233 mV under alkaline and acidic conditions, respectively. Depending on the diversity of POMs and MOFs, the current feasible and reliable MoP-QDs@PC electrocatalysts from PMo 12 @UiO-66 precursor would inspire more effective strategies to economical, efficient and stable electrocatalysts for hydrogen evolution.