Hydrogen Spillover-Bridged Volmer/Tafel Processes Enabling Ampere-Level Current Density Alkaline Hydrogen Evolution Reaction under Low Overpotential
Citations Over TimeTop 1% of 2022 papers
Abstract
Water-alkaline electrolysis holds a great promise for industry-scale hydrogen production but is hindered by the lack of enabling hydrogen evolution reaction electrocatalysts to operate at ampere-level current densities under low overpotentials. Here, we report the use of hydrogen spillover-bridged water dissociation/hydrogen formation processes occurring at the synergistically hybridized Ni3S2/Cr2S3 sites to incapacitate the inhibition effect of high-current-density-induced high hydrogen coverage at the water dissociation site and concurrently promote Volmer/Tafel processes. The mechanistic insights critically important to enable ampere-level current density operation are depicted from the experimental and theoretical studies. The Volmer process is drastically boosted by the strong H2O adsorption at Cr5c sites of Cr2S3, the efficient H2O* dissociation via a heterolytic cleavage process (Cr5c-H2O* + S3c(#) → Cr5c-OH* + S3c-H#) on the Cr5c/S3c sites in Cr2S3, and the rapid desorption of OH* from Cr5c sites of Cr2S3 via a new water-assisted desorption mechanism (Cr5c-OH* + H2O(aq) → Cr5c-H2O* + OH-(aq)), while the efficient Tafel process is achieved through hydrogen spillover to rapidly transfer H# from the synergistically located H-rich site (Cr2S3) to the H-deficient site (Ni3S2) with excellent hydrogen formation activity. As a result, the hybridized Ni3S2/Cr2S3 electrocatalyst can readily achieve a current density of 3.5 A cm-2 under an overpotential of 251 ± 3 mV in 1.0 M KOH electrolyte. The concept exemplified in this work provides a useful means to address the shortfalls of ampere-level current-density-tolerant Hydrogen evolution reaction (HER) electrocatalysts.
Related Papers
- → 3D MoS2-rGO@Mo nanohybrids for enhanced hydrogen evolution: The importance of the synergy on the Volmer reaction(2018)56 cited
- → MoS 2 nanosheets on C 3 N 4 realizing improved electrochemical hydrogen evolution(2017)19 cited
- → Effect of the amount of nickel sulphide, molybdenum disulphide and carbon nanosupport on a Tafel slope and overpotential optimization(2017)18 cited
- → Co(Ni)–Mo–Sx Chalcogels Films as pH-Universal Electrocatalysts for the H2 Evolution Reaction(2019)6 cited
- → Acid-engineered defective MoS2 as an efficient electrocatalyst for hydrogen evolution reaction(2018)17 cited