Monolithic 3D Cross-Linked Polymeric Graphene Materials and the Likes: Preparation and Their Redox Catalytic Applications

Abstract

While there have been tremendous studies about graphene and its applications in the past decade, so far the proposed huge potential of this material has not been materialized. One of the prerequisites to overcome these challenges is maintaining the nature and intrinsic properties of individual graphene sheets while in the state of bulk material. Thus, in this Perspective contribution, the fabrication/synthesis of the monolithic polymeric and three-dimensional (3D) cross-linked bulk materials (3DGraphene) with (doped) 2D graphene sheets as the building block will first be briefly summarized. Then, the second part will cover the redox catalytic application of these bulk materials including doped 3DGraphene, the graphene-like material polymeric CN and their hybrid materials. These will include mainly oxygen reduction reactions (ORR), hydrogen evolution reactions (HER), and CO reduction for their latest development. Finally, challenges and outlook related to the design of 3D cross-linked graphene based materials and their catalytic applications will be briefly discussed.

Hot electron prompted highly efficient photocatalysis based on 3D graphene/non-precious metal nanoparticles

“…During this solvothermal process, the 3DGraphene network can be constructed via the covalent cross-linking of the functional groups such as OH, COOH, and epoxy groups mainly located on the GO sheets edges. 24,25 Simultaneously, the dispersed ZIF-67 crystals are spontaneously self-assembled on the surface of GO sheets through the non-covalent bond, such as hydrogen bonding between the H atoms of ZIF-67 and the -OH/-COOH of graphene sheets. The following freeze-drying process can keep the cross-linked 3D porous structure of the composites.…”

“…The SEM images ( Fig. 1a and b) exhibit the cross-linked 3DGraphene skeleton structures, originated from the efficient assembly of the wrinkled GO sheets during the hydrothermal process, 24,25 which is benecial for the formation of highly dispersed cobalt nanoparticles. As shown in the high magnied SEM image (Fig.…”

“…Monolithic three-dimensional (3D) cross-linked graphene (3DGraphene) bulk materials have attracted increasing interest as a support to load catalyst nanoparticles. 24,25 Such these composites could not only preserve the small size, high dispersibility and exposure of the active catalytic sites, but also possess suitable pore networks. Simultaneously, the multidimensional electron transport path-ways deliver an extraordinary electronic transport property in catalytic reactions.…”

Absorption of atomic and molecular species in carbon cellular structures (Review article)

“…These results propose CHs as novel magnetic carbon. Doped CHs are also perspective in the redox catalytic applications of these bulk materials [43,44]. These include oxygen reduction reactions, hydrogen evolution reactions, and CO 2 reduction.…”

Nonmainstream Out‐Plane Fluoro‐ and Amino‐Cofunctionalized Graphene for a Striking Electrocatalyst: Programming Substitutive/Reductive Defluorination toward Graphite Fluoride

“…Heteroatom functionalization toward pristine graphene can finely modulate the electronic structure, engineer the bandgap, manipulate the interfacial characteristics, improve its solution processability, or even bestow graphene some totally new properties, and thus greatly promises graphene reachable in diversified applications, such as catalysis, energy conversion and storage, nanoelectronics, cancer diagnosis and therapy, solar vapor generation, and desalination . Many quite exciting examples reveal that graphene exerts largely enhanced electrocatalytic activities in oxygen reduction/evolution, hydrogen evolution reactions (ORR, OER, and HER) when serving as a metal‐free catalyst after its honeycomb lattice doped with nitrogen (N) .…”