Effects of Intrinsic Pentagon Defects on Electrochemical Reactivity of Carbon Nanomaterials

Abstract

Theoretical calculations reveal that intrinsic pentagons in the basal plane can contribute to the local electronic redistribution and the contraction of band gap,m aking the carbon matrix possess superior binding affinity and electrochemical reactivity.T oe xperimentally verify this,apentagondefect-richc arbon nanomaterial was constructed by means of in situ etching of fullerene molecules (C 60 ). The electrochemical tests showt hat, relative to hexagons,s uch ac arbon-based material with abundant intrinsic pentagon defects makes much greater contribution to the electrocatalytic oxygen reduction activity and electric double layer capacitance.Itshows afourelectron-reaction mechanism similar to commercial Pt/C and other transition-metal-based catalysts,a nd ah igher specific capacitance than many reported metal-free carbon materials. These results showt he influence of intrinsic pentagon defects for developing carbon-based nanomaterials toward energy conversion and storage devices.

N,S‐Co‐Doped Porous Carbon Nanofiber Films Derived from Fullerenes (C60) as Efficient Electrocatalysts for Oxygen Reduction and a Zn–Air Battery

“…[19] More interestingly,arecents tudy demonstrated that fullerenes (C 60 )c an derive abundant pentagond efects, which offer great potentiala sh igh-efficiency ORR catalysts. [9,20] As displayed in Figure S3 b, N,S-PCNFs show ab road Db and and ah igh D-to-Gi ntensity ratio (I D /I G = 1.08), indicating al ow degree of graphitization and abundant defects, whichm ay be favorable for the ORR. [21] N 2 adsorption/desorption isotherms were collectedt oe xplore the pore structures and specific surface areas of the asprepared samples.…”

“…[8a] Mu and co-workers cut C 60 molecules into fragments by KOH activation to construct ap entagon-defect-rich carbon nanomaterial that showed significant electrocatalytic oxygen reduction activity. [9] However, the reported methods usually involvet edious procedures and materiall oss during the removal of templates or activators (e.g.,K OH), and the ORR performances of such fullerene-derived carbon materials are still inferior. Therefore, other efficient and facile methods to create high-efficiency fullerenederived ORR electrocatalysts are required.…”

Nitrogen‐Doped Porous Carbon Supported Nonprecious Metal Single‐Atom Electrocatalysts: from Synthesis to Application

“…For the efficient use and sustainable development of energy, it is necessary to find nonprecious metal catalysts that can replace Pt. With the development of supported nonprecious metal nanocatalysts and the effect of size on catalysis, nonprecious metal single‐atom catalysts with highly exposed active sites have been developed as promising candidates for alternative Pt‐based catalysts . Nonprecious metal single‐atom catalyst materials have clear single active sites, unsaturated coordination environment.…”

Unprecedented Nonphotomediated Hole (h+) Oxidation System Constructed from Defective Carbon Nanotubes and Superoxides

“…Previous theoretical calculations indicated that the enhancement of the charge or/and spin density of carbon materials could promote catalytic performance due to the increased adsorption affinity of oxidant molecules. 16 , 17 Recently, the intrinsic defect engineering has been regarded as an effective strategy, including the introduction of zigzag/armchair edges, vacancies, or topological defects (e.g., pentagons, heptagons, and Stone–Wales). 18 − 23 The defect sites can significantly tailor the surface electronic structures and act as charge-carrier acceptors, which might facilitate oxidant activation by the transfer of the electrons to the adsorbed oxidant molecules.…”