Engineering Lattice Oxygen Activation of Iridium Clusters Stabilized on Amorphous Bimetal Borides Array for Oxygen Evolution Reaction

Abstract

Developing robust oxygen evolution reaction (OER) catalysts requires significant advances in material design and in-depth understanding for water electrolysis. Herein, we report iridium clusters stabilized surface reconstructed oxyhydroxides on amorphous metal borides array, achieving an ultralow overpotential of 178 mV at 10 mA cm À2 for OER in alkaline medium. The coupling of iridium clusters induced the formation of high valence cobalt species and Ir-O-Co bridge between iridium and oxyhydroxides at the atomic scale,engineering lattice oxygen activation and non-concerted proton-electron transfer to trigger multiple active sites for intrinsic pH-dependent OER activity.T he lattice oxygen oxidation mechanism (LOM) was confirmed by in situ 18 O isotope labeling mass spectrometry and chemical recognition of negative peroxo-like species.Theoretical simulations reveal that the OER performance on this catalyst is intrinsically dominated by LOM pathway,facilitating the reaction kinetics. This work not only paves an avenue for the rational design of electrocatalysts,b ut also serves the fundamental insights into the lattice oxygen participation for promising OER application.

Activating the lattice oxygen oxidation mechanism in amorphous molybdenum cobalt oxide nanosheets for water oxidation

“…These parameters can be tuned by adjusting the catalyst bulk composition, introducing vacancies or extrinsic metal dopants. 17–20 More specifically, LOM can be particularly promoted through doping with high electronegative cations that facilitate the participation of lattice oxygen in the reaction. 21…”

Triggering Lattice Oxygen Activation of Single‐Atomic Mo Sites Anchored on Ni–Fe Oxyhydroxides Nanoarrays for Electrochemical Water Oxidation

“…This work may provide new insights for designing ideal electrocatalysts via tuning the chemical state and activating the anions ligands. catalysts via triggering the lattice oxygen redox cycles, such as Co-based perovskite and spinel oxides, [7][8][9][10][11][12][13] as well as Mn-based oxides. [4,[14][15][16] Overall, it presents great potential for discovering catalysts with unique electronic configuration and suitable reactivity of lattice oxygen.…”

“…The activation of lattice oxygen avoids the intrinsic scaling limitations in AEM, which is crucial for the overpotential decrement. In fact, previous works have shown that the electrocatalytic activities were considerably improved for bimetallic and multimetallic catalysts via triggering the lattice oxygen redox cycles, such as Co‐based perovskite and spinel oxides, [ 7–13 ] as well as Mn‐based oxides. [ 4,14–16 ] Overall, it presents great potential for discovering catalysts with unique electronic configuration and suitable reactivity of lattice oxygen.…”

Molecular Mechanism of the Mononuclear Copper Complex‐Catalyzed Water Oxidation from Cluster‐Continuum Model Calculations

“…This process is energetically uphill and requires a high overpotential of 1.23 V vs. standard hydrogen electrode (SHE). [1][2][3][4][5][6] In the last several decades, numerous efforts have been made in developing transition metal complex-based water oxidation catalysts (WOCs), [7][8][9][10][11][12] such as ruthenium, [13][14][15][16][17][18][19][20][21][22][23] iridium, [24][25][26][27] vanadium, [28] manganese, [29][30][31][32][33][34][35] iron, [36][37][38][39][40][41][42] cobalt, [43][44][45][46][47][48][49][...…”

“…In the last several decades, numerous efforts have been made in developing transition metal complex‐based water oxidation catalysts (WOCs), [7–12] such as ruthenium, [13–23] iridium, [24–27] vanadium, [28] manganese, [29–35] iron, [36–42] cobalt, [43–51] nickel, [52–58] and copper complexes [59–67] . Since the report of the first molecular copper WOC in 2012 by Mayer and co‐workers, [60] the copper‐based molecular catalysts have received growing attention due to the advantages of their low cost and rich redox properties.…”