Formation of Ni-Fe Mixed Diselenide Nanocages as a Superior Oxygen Evolution Electrocatalyst

The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.

Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (∼20 nm) are electrochemically transformed into ultra-small diameter (2–5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeO x nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm−2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts.

Cost-effective production of solar fuels requires robust and earth-abundant oxygen evolution reaction (OER) catalysts. Herein, we report that ultrathin nanoplates of cobalt-manganese layered double hydroxide (CoMn LDH) are a highly active and stable oxygen evolution catalyst. The catalyst was fabricated by a one-pot coprecipitation method at room temperature, and its turnover frequency (TOF) is more than 20 times higher than the TOFs of Co and Mn oxides and hydroxides, and 9 times higher than the TOF of a precious IrO2 catalyst. The activity of the catalyst was promoted by anodic conditioning, which was proposed to form amorphous regions and reactive Co(IV) species on the surface. The stability of the catalyst was demonstrated by continued electrolysis.