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Title: Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons

Abstract

Graphene nanoribbons (GNRs) can be synthesized from molecular precursors with atomic precision. A prominent case is the 7-atom-wide armchair GNR made from 10,10'-dibromo-9,9'-bianthryl (DBBA) precursors on metal substrates through dehalogenation/polymerization followed by cyclodehydrogenation. We investigate the key aspects of the cyclodehydrogenation process by evaluating the energy profiles of various reaction pathways using density functional theory and the nudged elastic band method. The metal substrate plays a critical catalytic role by providing stronger adsorption for products and facilitating H desorption. For polyanthrylene on an extra layer of GNR on Au, the underlying GNR insulates it from the Au substrate and increases the reaction barriers, rendering the polyanthrylene “quasi-freestanding”. However, positive charge injection can induce localized cyclodehydrogenation. We find that this is due to the stabilization of an intermediate state through an arenium ion mechanism and favorable orbital symmetries. These results provide mechanistic insight into the effects of the metal substrate and charge injection on cyclodehydrogenation during GNR synthesis and offer guidance for the design and growth of new graphitic structures.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. North Carolina State Univ., Raleigh, NC (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1560393
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Xiao, Zhongcan, Ma, Chuanxu, Lu, Wenchang, Huang, Jingsong, Liang, Liangbo, Hong, Kunlun, Li, An -Ping, Sumpter, Bobby G., and Bernholc, Jerzy. Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons. United States: N. p., 2019. Web. doi:10.1038/s41524-019-0228-6.
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Xiao, Zhongcan, Ma, Chuanxu, Lu, Wenchang, Huang, Jingsong, Liang, Liangbo, Hong, Kunlun, Li, An -Ping, Sumpter, Bobby G., & Bernholc, Jerzy. Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons. United States. https://doi.org/10.1038/s41524-019-0228-6
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Xiao, Zhongcan, Ma, Chuanxu, Lu, Wenchang, Huang, Jingsong, Liang, Liangbo, Hong, Kunlun, Li, An -Ping, Sumpter, Bobby G., and Bernholc, Jerzy. Fri . "Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons". United States. https://doi.org/10.1038/s41524-019-0228-6. https://www.osti.gov/servlets/purl/1560393.
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@article{osti_1560393,
title = {Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons},
author = {Xiao, Zhongcan and Ma, Chuanxu and Lu, Wenchang and Huang, Jingsong and Liang, Liangbo and Hong, Kunlun and Li, An -Ping and Sumpter, Bobby G. and Bernholc, Jerzy},
abstractNote = {Graphene nanoribbons (GNRs) can be synthesized from molecular precursors with atomic precision. A prominent case is the 7-atom-wide armchair GNR made from 10,10'-dibromo-9,9'-bianthryl (DBBA) precursors on metal substrates through dehalogenation/polymerization followed by cyclodehydrogenation. We investigate the key aspects of the cyclodehydrogenation process by evaluating the energy profiles of various reaction pathways using density functional theory and the nudged elastic band method. The metal substrate plays a critical catalytic role by providing stronger adsorption for products and facilitating H desorption. For polyanthrylene on an extra layer of GNR on Au, the underlying GNR insulates it from the Au substrate and increases the reaction barriers, rendering the polyanthrylene “quasi-freestanding”. However, positive charge injection can induce localized cyclodehydrogenation. We find that this is due to the stabilization of an intermediate state through an arenium ion mechanism and favorable orbital symmetries. These results provide mechanistic insight into the effects of the metal substrate and charge injection on cyclodehydrogenation during GNR synthesis and offer guidance for the design and growth of new graphitic structures.},
doi = {10.1038/s41524-019-0228-6},
journal = {npj Computational Materials},
number = 1,
volume = 5,
place = {United States},
year = {2019},
month = {9}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1038/s41524-019-0228-6
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Figures / Tables:

Fig. 1 Fig. 1: Optimized atomic structures (top panels), simulated (middle panels), and experimental (bottom panels) STM images for a polyanthrylene on Au, b GNR on Au, c polyanthrylene on GNR-Au, and d polyanthrylene-GNR heterojunction on GNR-Au. The experimental and simulated STM images are obtained at a sample bias of −2.0 V
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