Lattice Strain Mediated Reversible Reconstruction in CoMoO4·0.69H2O for Intermittent Oxygen Evolution.

ABSTRACT

A heterogeneous interface usually plays a versatile role in modulating catalysis and the durability of hybrid electrocatalysts for oxygen evolution reaction (OER), and its intrinsic mechanism is still in dispute due to an uncertain correlation of initial, intermediate and active phases. In this article, the CoMoO4·0.69H2O/Co3O4 heterogeneous interface is configured to understand the evolution kinetics of these correlated phases. Due to the chemically and electrochemically "inert" character of Co3O4 support, lattice strain with 3.31% tuning magnitude in primary CoMoO4·0.69H2O can be inherited after spontaneous dissolution of molybdenum cations in electrolyte, dominating catalytic activity of the reconstructed CoOOH. In situ Raman spectroscopy demonstrates reversible conversion between active CoOOH and amorphous cobalt oxide during OER when positive and negative potentials are sequentially supplied onto hybrid catalysts with favorable strain. Therefore, superior durability with negligible decay after 10 cycles is experimentally identified for intermittent oxygen evolution. Theoretical calculations indicate that appropriate stress within the electrocatalyst could reduce the reaction energy barrier and enhance the OER performance by optimizing the adsorption of intermediates.