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Updated: Oct 28, 2025

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Reversible Ligand Exchange in Atomically Dispersed Catalysts for Modulating the Activity and Selectivity of the
Jae Hyung Kim1, Dongyup Shin2, Jinjong Kim3
1School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST-gil, Ulsan, 44919, Republic of Korea.
Abstract:
Rational control of the coordination environment of atomically dispersed catalysts is pivotal to achieve desirable catalytic reactivity. We report the reversible control of coordination structure in atomically dispersed electrocatalysts via ligand exchange reactions to reversibly modulate their reactivity for oxygen reduction reaction (ORR). The CO-ligated atomically dispersed Rh catalyst exhibited ca. 30-fold higher ORR activity than the NHx -ligated catalyst, whereas the latter showed three times higher H2 O2 selectivity than the former. Post-treatments of the catalysts with CO or NH3 allowed the reversible exchange of CO and NHx ligands, which reversibly tuned oxidation state of metal centers and their ORR activity and selectivity. DFT calculations revealed that more reduced oxidation state of CO-ligated Rh site could further stabilize the *OOH intermediate, facilitating the two- and four-electron pathway ORR. The reversible ligand exchange reactions were generalized to Ir- and Pt-based catalysts.
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