Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production

摘要

Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm(-2) with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni-2-S-1" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni-2-S-1" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity. @@@ The sluggish water activation kinetics and instability of metal-organic frameworks for hydrogen evolution reaction limit their industrial applications. Here, authors construct a unique triangular active region to accelerate the crucial water activation and stabilize metal-organic frameworks.

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