Proposal of spin crossover as a reversible switch of catalytic activity for the oxygen evolution reaction in two dimensional metal-organic frameworks.

The development of oxygen evolution reaction (OER) catalysts with high activity and controllability is crucial for clean energy conversion and storage but remains a challenge. Here, based on first-principles calculations, we propose to utilize spin crossover (SCO) in two-dimensional (2D) metal-organic frameworks (MOFs) to achieve reversible control of OER catalytic activity. The theoretical design of a 2D square lattice MOF with Co as nodes and tetrakis-substituted cyanimino squaric acid (TCSA) as ligands, which transforms between the high spin (HS) and the low spin (LS) state by applying an external strain (∼2%), confirms our proposal. In particular, the HS-LS spin state transition of Co(TCSA) considerably regulates the adsorption strength of the key intermediate HO* in the OER process, resulting in a significant reduction of the overpotential from 0.62 V in the HS state to 0.32 V in the LS state, thus realizing a reversible switch for the activity of the OER. Moreover, the high activity of the LS state is confirmed by microkinetic and constant potential method simulations.