Programming Structural Disorder in MOFs for a Stable Bifunctional Water‐Splitting Electrocatalyst

ABSTRACT

For practical water electrolysis, electrocatalysts must deliver both high activity and stability. Metal–organic frameworks (MOFs) provide a programmable platform for constructing tailored active sites and coordination environments, offering considerable potential for high activity. However, MOF electrocatalysts typically undergo activation‐induced reconstruction, during which their ordered frameworks transform into disordered active states, generating reconstruction‐induced strain. Poor accommodation of this strain can lead to morphological collapse, metal‐site leaching, and ultimately compromised stability. To address these issues, we leveraged the programmability of MOFs to restrict the long‐range extension of their secondary building units, thereby pre‐introducing disorder into the framework to facilitate strain accommodation during reconstruction. Consequently, activation increased the electrochemically active surface area of the disordered structure, in contrast to the decrease observed for the ordered counterpart, suggesting that destructive reconstruction was effectively mitigated. The resulting active phase retained M–O–M bridging vibrational features even at 1.9 V (vs. RHE), whereas the corresponding features in the ordered MOF were markedly weakened at 1.4 V (vs. RHE), indicating better structural integrity after reconstruction. These advantages enabled stable operation for up to 500 h in an electrolyzer and 1500 h at 1 A cm ⁻² in a two‐electrode cell, demonstrating excellent durability for overall water splitting.