Abstract
The ability to develop highly active and low-cost electrocatalysts represents an important endeavor toward accelerating sluggish water-oxidation kinetics. Herein, we report, for the first time, the implementation and unravelling of photothermal effect of spinel nanoparticles (NPs) on promoting dynamic active sites generation to markedly enhance their oxygen evolution reaction (OER) activity via an integrated operando Raman and density functional theory (DFT) study. Specifically, NiFe2O4 (NFO) NPs are first synthesized by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors. Upon the NIR light irradiation, the photothermal heating of the NFO-based electrode progressively raises the temperature, accompanied by a marked decrease of overpotential. Accordingly, only an overpotential of 309 mV is required to yield a high current density of 100 mA cm-2, greatly lower than recently-reported earth-abundant electrocatalysts. More importantly, photothermal effect of NFO NPs not only significantly reduces the activation energy necessitated for water splitting, but also facilitates surface reconstruction into high-active oxyhydroxides at lower potential (1.36 V) under OER conditions, as revealed by operando Raman spectra-electrochemistry. Moreover, the DFT calculation corroborates that these reconstructed (Ni,Fe)oxyhydroxides are electrocatalytically active sites as the kinetics barrier is largely reduced over pure NFO without surface reconstruction. Given the diversity of materials (metal oxides, sulfides, phosphides, etc.) possessing the photo-to-thermal conversion, this effect may thus provide a unique and robust platform to boost highly-active surface species in nanomaterials for fundamental understanding of enhanced performance that may underpin future advances in electrocatalysis, photocatalysis, solar energy conversion and renewable energy production.
Mastering Surface Reconstruction of Metastable Spinel Oxides for Better Water Oxidation
