Current
energy and environmental challenges demand the development
and design of multifunctional porous materials with tunable properties
for catalysis, water purification, and energy conversion and storage.
Because of their amenability to de novo reticular chemistry, metal–organic
frameworks (MOFs) have become key materials in this area. However,
their usefulness is often limited by low chemical stability, conductivity
and inappropriate pore sizes. Conductive two-dimensional (2D) materials
with robust structural skeletons and/or functionalized surfaces can
form stabilizing interactions with MOF components, enabling the fabrication
of MOF nanocomposites with tunable pore characteristics. Graphene
and its functional derivatives are the largest class of 2D materials
and possess remarkable compositional versatility, structural diversity,
and controllable surface chemistry. Here, we critically review current
knowledge concerning the growth, structure, and properties of graphene
derivatives, MOFs, and their graphene@MOF composites as well as the
associated structure–property–performance relationships.
Synthetic strategies for preparing graphene@MOF composites and tuning
their properties are also comprehensively reviewed together with their
applications in gas storage/separation, water purification, catalysis
(organo-, electro-, and photocatalysis), and electrochemical energy
storage and conversion. Current challenges in the development of graphene@MOF
hybrids and their practical applications are addressed, revealing
areas for future investigation. We hope that this review will inspire
further exploration of new graphene@MOF hybrids for energy, electronic,
biomedical, and photocatalysis applications as well as studies on
previously unreported properties of known hybrids to reveal potential
“diamonds in the rough”.