Promoting Bifunctional Water Splitting by Modification of the Electronic Structure at the Interface of NiFe Layered Double Hydroxide and Ag

Electrochemical water splitting is a promising method for the renewable production of high-purity hydrogen via the hydrogen evolution reaction (HER). Ni−Fe layered double hydroxides (Ni−Fe LDHs) are highly efficient materials for mediating the oxygen evolution reaction (OER), a half-reaction for water splitting at the anode, but LDHs typically display poor HER performance. Here, we report the preparation of self-organized Ag@NiFe layered double hydroxide core-shell electrodes on Ni foam (Ag@NiFe/NF) prepared by galvanic etching for mediating both the HER and OER (bifunctional water-splitting electrocatalysis). This synthetic strategy allowed for the preparation of organized hierarchical architectures which displayed improved the electrochemical performance by tuning the electronic structure of the catalyst and increasing the surface area utilization. X-ray photoelectron spectroscopy (XPS) and theoretical calculations revealed that electron transfer from the Ni−Fe LDH to Ag influenced the adsorption of the reaction intermediates leading to enhanced catalytic activity. The Ag@NiFe/NF electrode displayed overpotentials as low as 180 and 80 mV for oxygen and hydrogen evolution, respectively, at a current density of 10 mA cm–2, and improvements in the specific activity by ∼5× and ∼1.5× for the oxygen and hydrogen evolution reaction, respectively, compared to benchmark NiFe hydroxide materials. Additionally, an integrated water-splitting electrolyzer electrode can be driven by an AA battery.