Asymmetric Coordination of Iridium Single-atom IrN3O Boosting Formic Acid Oxidation Catalysis

Rational design of the proximal coordination of an active site to achieve its optimum catalytic activity is the ultimate goal in single-atom catalysis, but still challenging. Here, we report theoretical prediction and experimental realization of an asymmetrically coordinated iridium single-atom catalyst (IrN₃O) for the formic acid oxidation reaction (FAOR). Theoretical calculations reveal that the substitution of one or two nitrogen with more electronegative oxygen in the symmetric IrN₄ motif splits and downshifts the Ir 5d orbitals with respect to the Fermi level, moderating the binding strength of key intermediates on IrN_4−xO_x (x=1, 2) sites, especially that the IrN₃O motif shows ideal activity for FAOR with a near-zero overpotential. The as-designed asymmetric Ir motifs were realized by pyrolyzing Ir precursor with oxygen-rich glucose and nitrogen-rich melamine, exhibiting a mass activity of 25 and 87 times greater than those of state-of-the-art Pd/C and Pt/C, respectively.