Layered double hydroxides with atomic-scale defects for superior electrocatalysis

Atomic composition tuning and defect engineering are effective strategies toenhance the catalytic performance of multicomponent catalysts by improvingthe synergetic effect; however, it remains challenging to dramatically tune the active sites on multicomponent materials through simultaneous defect engineeringat the atomic scale because of the similarities of the local environment. Herein,using the oxygen evolution reaction (OER) as a probe reaction, we deliberatelyintroduced base-soluble Zn(II) or Al(III) sites into NiFe layered double hydroxides(LDHs), which are one of the best OER catalysts. Then, the Zn(II) or Al(III) siteswere selectively etched to create atomic M(II)/M(III) defects, which dramaticallyenhanced the OER activity. At a current density of 20 mA·cm−2, only 200 mV overpotential was required to generate M(II) defect-rich NiFe LDHs, which is the best NiFe-based OER catalyst reported to date. Density functional theory(DFT) calculations revealed that the creation of dangling Ni–Fe sites (i.e., unsaturated coordinated Ni–Fe sites) by defect engineering of a Ni–O–Fe site at the atomic scale efficiently lowers the Gibbs free energy of the oxygen evolutionprocess. This defect engineering strategy provides new insights into catalysts atthe atomic scale and should be beneficial for the design of a variety of catalysts.