The electrocatalytic activity of heteroatom-doped carbon-based nanomaterials has become a growing interest in the past few years due to their potential applications for fuel cells and metal-air batteries. Hitherto, several approaches have been exploited for the doping of heteroatoms into graphitic structure, but they are feasible for the scalable production of heteroatom-doped carbon nanomaterials due to high manufacturing costs and technical difficulties.
Researchers in Ulsan National Institute of Science and Technology(UNIST), South Korea, paved the way to a simple, but efficient and eco-friendly production of edge-selectively functionalized graphene nanoplatelets (EFGnPs) with different edge groups by simply dry ball milling graphite in the presence of various gases or gas mixture.
Due to the versatility of mechanochemical reactions driven by ball milling, various functional groups could be introduced at the broken edges of graphene nanoplatelets (GnPs) in the presence of appropriate chemical vapors , liquids, or solids in the ball-mill crusher.
The mechanism of edge-selective functionalization in the ball-milling process involves the reaction between reactive carbon species generated by a mechanochemical cleavage of graphitic C-C bonds and gases in a sealed ball-mill crusher. The dormant active carbon species, which are unreacted in the crusher, could be terminated by subsequent exposure to air moisture. As a result, some oxygenated groups, such as hydroxyl (-OH) and carboxylic acid (-COOH), could be introduced at the broken edges of the preformed EFGnPs with minimal basal plane distortion
A scanning electron microscope (SEM) is used to demonstrate the mechanochemical cracking of a large grain size of graphite into a small grain size of EFGnPs. Due to the reaction between the newly formed active carbon species at the broken edges of the GnPs and corresponding gases, the ball milling and subsequent workup procedures were found to increase the weight of all the resultant EFGnPs with respect to the graphite starting material. These results indicated that the mechanochemical functionalization of graphite was efficient. The resultant EFGnPs are active enough for the oxygen reduction reaction (ORR) in fuel cells, and hence they will make expensive platinum (Pt)-based electrocatalysts to take a back seat.
Jong-Beom Baek, professor and director of the Interdisciplinary School of Green Energy/Low-Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology(UNIST), Ulsan, South Korea, led this work.
"We have developed a simple, but versatile ball-milling process to efficiently exfoliate the pristine graphite directly into EFGnPs. Various microscopic and spectroscopic measurements were performed to confirm the reaction mechanisms for the edge functionalization of graphite by ball milling in the presence of corresponding gases and their superior electrocatalytic activities of the ORR," said Prof. Baek.
This research was funded by the Ministry of Education, Science and Technology (Minister Lee Ju-Ho) through the National Research Foundation of Korea (President Seung Jong Lee) and published in Journal of the American Chemical Society (Title: Large-scale production of edge-selectively functionalized graphene nanoplatelets via ball-milling and their use as metal-free electrocatalysts for oxygen reduction reaction).
Source and top image: UNIST
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