Elaborate Designed Three‐Dimensional Hierarchical Conductive MOF/LDH/CF Nanoarchitectures for Superior Capacitive Deionization

Abstract Rational exploration of cost‐effective, durable, and high‐performance electrode materials is imperative for advancing the progress of capacitive deionization (CDI). The integration of multicomponent layered double hydroxides (LDHs) with conjugated conductive metal–organic frameworks ( c ‐MOFs) to fabricate bifunctional heterostructure electrode materials is considered a complex but promising strategy. Herein, the fabrication of elaborately designed three‐dimensional hierarchical conductive MOF/LDH/CF nanoarchitectures (M–CAT/LDH/CF) as CDI anodes via a controllable grafted‐growth strategy is reported. In this assembly, carbon fiber (CF) provides exceptional electrical conductivity facilitating rapid ion transfer and acts as a sturdy foundation for even distribution of NiCoCu‐LDH nanosheets. Moreover, the well‐ordered NiCoCu‐LDH further acts as interior templates to create an interface by embedding c‐MOFs and aligning two crystal lattice systems, facilitating the graft growth of c‐MOFs/LDH heterostructures along the LDH nanosheet arrays on CF, leading to accelerated ion diffusion kinetics. Density functional theory (DFT) confirms the unique structure of M–CAT/LDH/CF promotes interfacial charge transfer from NiCoCu‐LDH to M–CAT. This enhancement accelerates ion transfer, decreases ion migration energy, and leads to better ion diffusion kinetics and a smoother Cl − shuttle. Accordingly, the asymmetrical M–CAT/LDH/CF cell exhibited superior specific capacitance (315 F g −1 ), excellent salt adsorption capacity (147.8 mg g −1 ), rapid rate (21.1 mg g −1 min −1 ), and impressive cyclic stability (91.4 % retention rate). This work offers valuable insights for designing heterostructure electrode materials based on three‐dimensional interconnected networks, contributing to further advancements in CDI technology.