The development of efficient and low-cost electrocatalysts for oxygen evolution reaction is critical for improving the water electrolysis efficiency. Here we report a strategy using Fe substitution to enable the inactive spinel CoAl 2 O 4 to become highly active and superior to the benchmark IrO 2. The Fe substitution is revealed to facilitate the surface reconstruction into active Co oxyhydroxides under OER conditions. It also activates the deprotonation on the reconstructed oxyhydroxide to induce negatively charged oxygen as active site, thus significantly enhancing the OER activity of CoAl 2 O 4. Furthermore, it promotes the pre-oxidation of Co and introduces great structural flexibility due to the uplift of the O 2p levels. This results in an accumulation of surface oxygen vacancy along with lattice oxygen oxidation that terminates as Al 3+ leaches, preventing further reconstruction. We showcase a promising way to achieve tunable electrochemical reconstruction by optimizing the electronic structure for low-cost and robust spinel oxide OER catalysts.
The hydrogen evolution reaction (HER) is a half-cell reaction in water electrolysis for producing hydrogen gas. In industrial water electrolysis, the HER is often conducted in alkaline media to achieve higher stability of the electrode materials. However, the kinetics of the HER in alkaline medium is slow relative to that in acid because of the low concentration of protons in the former. Under the latter conditions, the entire HER process will require additional effort to obtain protons by water dissociation near or on the catalyst surface. Heterostructured catalysts, with fascinating synergistic effects derived from their heterogeneous interfaces, can provide multiple functional sites for the overall reaction process. At present, the activity of the most active known heterostructured catalysts surpasses (platinum-based heterostructures) or approaches (noble-metal-free heterostructures) that of the commercial Pt/C catalyst under alkaline conditions, demonstrating an infusive potential to break through the bottlenecks. This review summarizes the most representative and recent heterostructured HER catalysts for alkaline medium. The basics and principles of the HER under alkaline conditions are first introduced, followed by a discussion of the latest advances in heterostructured catalysts with/without noble-metal-based heterostructures. Special focus is placed on approaches for enhancing the reaction rate by accelerating the Volmer step. This review aims to provide an overview of the current developments in alkaline HER catalysts, as well as the design principles for the future development of heterostructured nano- or micro-sized electrocatalysts.
Spinel oxides have attracted growing interest over the years for catalysing the oxygen evolution reaction (OER) due to their efficiency and cost-effectiveness, but the fundamental understanding of the structure-property relationships remains elusive. Here we demonstrate that the OER activity on spinel oxides is intrinsically dominated by the covalency competition between tetrahedral and octahedral sites. The competition fabricates an asymmetric MT−O−MO backbone where the bond with weaker metal-oxygen covalency determines the exposure of cation sites and therefore the activity. Driven by this finding, a dataset with more than 300 spinel oxides is computed and used to train a machine learning model for screening the covalency competition in spinel oxides, with a mean absolute error of 0.05 eV. [Mn]T[Al0.5Mn1.5]OO4 is predicted to be a highly active OER catalyst and subsequent experimental results confirm its superior activity. This work sets mechanistic principles of spinel oxides for water oxidation, which may be extendable to other applications.
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