GO‐Assisted Growth of Accordion‐Like Multimetal MOF/GO Composite for Enhanced Electrochemical Energy Storage and Conversion

ABSTRACT

The controlled and scalable fabrication of multimetal metal–organic frameworks (MOFs) remains challenging due to differences in metal coordination kinetics and complex crystal evolution. Herein, a graphene oxide (GO)‐assisted one‐pot strategy is developed to prepare an accordion‐like NiCoFeCuZn‐MOF/GO composite assembled from single‐crystalline MOF nanosheets. Stepwise introduction of Ni, Co, Fe, Cu, and Zn into the BDC‐based MOF/GO platform (BDC = 1,4‐benzenedicarboxylic acid) reveals structural evolution. Tracking the growth process shows that GO promotes heterogeneous nucleation and multimetal incorporation. GO‐guided growth and the inherent two‐dimensional tendency of the Ni‐BDC framework facilitate layered structure formation. DFT calculations and compositional modulation indicate that unfavorable Cu/Zn substitution at exposed surface sites limits complete exfoliation during anti‐ripening, preserving partial interlayer contact and leading to the accordion‐like structure. The strategy enables kilogram‐scale preparation with preserved accordion‐like morphology and extends to NDC‐ and BPDC‐based systems (NDC = 2,6‐naphthalenedicarboxylic acid, BPDC = 4,4′‐biphenyldicarboxylic acid), demonstrating its generality. NiCoFeCuZn‐MOF/GO delivers 223.3 mA h g ⁻¹ at 1 mA cm ⁻² in a quasi‐solid‐state zinc battery and requires an overpotential of 213 mV to reach 10 mA cm ⁻² for the OER. These findings provide guidance for controlled growth of multimetal MOF/GO composites for electrochemical energy storage and conversion.