摘要
Graphene-based frameworks suffer from a low quantum capacitance due to graphene’s Dirac point at the Fermi level.This theoretical study investigated the effect structural defects,nitrogen and boron doping,and surface epoxy/hydroxy groups have on the electronic structure and capacitance of graphene.Density functional theory calculations reveal that the lowest energy configurations for nitrogen or boron substitutional doping occur when the dopant atoms are segregated.This elucidates why the magnetic transition for nitrogen doping is experimentally only observed at higher doping levels.We also highlight that the lowest energy configuration for a single vacancy defect is magnetic.Joint density functional theory calculations show that the fixed band approximation becomes increasingly inaccurate for electrolytes with lower dielectric constants.The introduction of structural defects rather than nitrogen or boron substitutional doping,or the introduction of adatoms leads to the largest increase in density of states and capacitance around graphene’s Dirac point.However,the presence of adatoms or substitutional doping leads to a larger shift of the potential of zero charge away from graphene’s Dirac point.
基金
supported partially by JST SICORP(Grant No.JPMJSC2112)
JST Adaptable and Seamless Technology Transfer Program through Target-driven R&D(A-STEP)(Grant No.JPMJTR22T6),and JSPS KAKENHI(Grant No.22K14757)
Calculations were performed using the U.K.National Supercomputing Facility ARCHER2(http://www.archer2.ac.uk)via our membership of the U.K.’s HEC Materials Chemistry Consortium,which is funded by the EPSRC(Grant Nos.EP/L000202 and EP/R029431)
the Molecular Modelling Hub for computational resources,MMM Hub,which is partially funded by EPSRC(Grant No.EP/P020194/1).This research has also utilized Queen Mary’s Apocrita HPC facility,supported by QMUL Research-IT.
