Revisiting the link between magnetic properties and chemisorption at graphene nanoribbon zigzag edge

Wei, Ziyang; Sautet, Philippe

doi:10.1063/5.0079064

Revisiting the link between magnetic properties and chemisorption at graphene nanoribbon zigzag edge

Journal Article · Wed Jan 26 23:00:00 EST 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0079064· OSTI ID:1979019

Wei, Ziyang ^[1]; ^[2]

University of California, Los Angeles, CA (United States); Univ. of California, Los Angeles, CA (United States)
University of California, Los Angeles, CA (United States)

Graphene has received tremendous interest in both chemical and physical fields. Among different edges of the graphene system, the zigzag edge terminated graphene nanoribbons (ZGNRs) show unique magnetic properties in the antiferromagnetic (AFM) state. However, to date, the understanding of ZGNR chemical properties is mainly based on the partial radical concept, and in previous studies, the energy differences between the ferromagnetic (FM) and AFM states are smaller than experimental evidence. Here, we report that the strongly constrained and appropriately normed functional gives a significantly larger energy difference, which matches the experimental observation. Furthermore, utilizing the energetics in the large difference case, we propose a conceptual supplement to the previous partial radical concept: the overall stabilization of the AFM state compared to the nonmagnetic (NM) state consists of two parts that affect the adsorption energy conversely. The NM-FM energy differences will strengthen the adsorption, being in line with the previous partial radical concept. The FM-AFM energy differences will instead weaken the adsorption. Here, we perform calculations of H, OH, and LiS radical adsorption energies on ZGNRs to show that this weakening effect is numerically non-negligible: at least a ~0.2 eV difference in the adsorption energies is found. We expect that this refinement of the partial radical concept can provide a more comprehensive understanding of the chemical properties of ZGNRs. The differences in adsorption energies for the H, OH, and LiS radicals found here lead to significant changes in the predicted reactivity of the ZGNR models.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0019381

OSTI ID:: 1979019

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 156; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (44)

Graphitic polymer strips with edge states Klein, D. J. Chemical Physics Letters, Vol. 217, Issue 3 https://doi.org/10.1016/0009-2614(93)e1378-t	journal	January 1994
N-doped graphene as catalysts for oxygen reduction and oxygen evolution reactions: Theoretical considerations Li, Mingtao; Zhang, Lipeng; Xu, Quan Journal of Catalysis, Vol. 314 https://doi.org/10.1016/j.jcat.2014.03.011	journal	May 2014
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction Kulkarni, Ambarish; Siahrostami, Samira; Patel, Anjli Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00488	journal	December 2017
Honeycomb Carbon: A Review of Graphene Allen, Matthew J.; Tung, Vincent C.; Kaner, Richard B. Chemical Reviews, Vol. 110, Issue 1, p. 132-145 https://doi.org/10.1021/cr900070d	journal	January 2010
Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300227s	journal	July 2012
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Half-metallic graphene nanoribbons Son, Young-Woo; Cohen, Marvin L.; Louie, Steven G. Nature, Vol. 444, Issue 7117 https://doi.org/10.1038/nature05180	journal	November 2006
A roadmap for graphene Novoselov, K. S.; Fal′ko, V. I.; Colombo, L. Nature, Vol. 490, Issue 7419 https://doi.org/10.1038/nature11458	journal	October 2012
Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons Magda, Gábor Zsolt; Jin, Xiaozhan; Hagymási, Imre Nature, Vol. 514, Issue 7524 https://doi.org/10.1038/nature13831	journal	October 2014
On-surface synthesis of graphene nanoribbons with zigzag edge topology Ruffieux, Pascal; Wang, Shiyong; Yang, Bo Nature, Vol. 531, Issue 7595 https://doi.org/10.1038/nature17151	journal	March 2016
Direct experimental determination of onset of electron–electron interactions in gap opening of zigzag graphene nanoribbons Li, Y. Y.; Chen, M. X.; Weinert, M. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5311	journal	July 2014
Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene Jiao, Yan; Zheng, Yao; Davey, Kenneth Nature Energy, Vol. 1, Issue 10 https://doi.org/10.1038/nenergy.2016.130	journal	September 2016
Hydrogen evolution: Guiding principles Xia, Zhenhai Nature Energy, Vol. 1, Issue 10 https://doi.org/10.1038/nenergy.2016.155	journal	September 2016
Computational high-throughput screening of electrocatalytic materials for hydrogen evolution Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob Nature Materials, Vol. 5, Issue 11, p. 909-913 https://doi.org/10.1038/nmat1752	journal	October 2006
Catalysis with two-dimensional materials and their heterostructures Deng, Dehui; Novoselov, K. S.; Fu, Qiang Nature Nanotechnology, Vol. 11, Issue 3 https://doi.org/10.1038/nnano.2015.340	journal	March 2016
Graphene plasmonics Grigorenko, A. N.; Polini, M.; Novoselov, K. S. Nature Photonics, Vol. 6, Issue 11, p. 749-758 https://doi.org/10.1038/nphoton.2012.262	journal	November 2012
A fundamental look at electrocatalytic sulfur reduction reaction Peng, Lele; Wei, Ziyang; Wan, Chengzhang Nature Catalysis, Vol. 3, Issue 9 https://doi.org/10.1038/s41929-020-0498-x	journal	August 2020
Stabilization mechanism of edge states in graphene Sasaki, K.; Murakami, S.; Saito, R. Applied Physics Letters, Vol. 88, Issue 11 https://doi.org/10.1063/1.2181274	journal	March 2006
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
Unique chemical reactivity of a graphene nanoribbon’s zigzag edge Jiang, De-en; Sumpter, Bobby G.; Dai, Sheng The Journal of Chemical Physics, Vol. 126, Issue 13 https://doi.org/10.1063/1.2715558	journal	April 2007
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional Ernzerhof, Matthias; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 110, Issue 11 https://doi.org/10.1063/1.478401	journal	March 1999
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
Density functional methods for the magnetism of transition metals: SCAN in relation to other functionals Fu, Yuhao; Singh, David J. Physical Review B, Vol. 100, Issue 4 https://doi.org/10.1103/physrevb.100.045126	journal	July 2019
Self-interaction correction to density-functional approximations for many-electron systems Perdew, J. P.; Zunger, Alex Physical Review B, Vol. 23, Issue 10, p. 5048-5079 https://doi.org/10.1103/physrevb.23.5048	journal	May 1981
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/physrevb.47.558	journal	January 1993
Electronic structure of a stepped graphite surface Kobayashi, Katsuyoshi Physical Review B, Vol. 48, Issue 3 https://doi.org/10.1103/physrevb.48.1757	journal	July 1993
Edge state in graphene ribbons: Nanometer size effect and edge shape dependence Nakada, Kyoko; Fujita, Mitsutaka; Dresselhaus, Gene Physical Review B, Vol. 54, Issue 24 https://doi.org/10.1103/physrevb.54.17954	journal	December 1996
Electronic and magnetic properties of nanographite ribbons Wakabayashi, Katsunori; Fujita, Mitsutaka; Ajiki, Hiroshi Physical Review B, Vol. 59, Issue 12 https://doi.org/10.1103/physrevb.59.8271	journal	March 1999
Graphitic ribbons without hydrogen-termination: Electronic structures and stabilities Kawai, Takazumi; Miyamoto, Yoshiyuki; Sugino, Osamu Physical Review B, Vol. 62, Issue 24 https://doi.org/10.1103/physrevb.62.r16349	journal	December 2000
Spin- and charge-polarized states in nanographene ribbons with zigzag edges Yamashiro, Atsushi; Shimoi, Yukihiro; Harigaya, Kikuo Physical Review B, Vol. 68, Issue 19 https://doi.org/10.1103/physrevb.68.193410	journal	November 2003
Magnetic ordering at the edges of graphitic fragments: Magnetic tail interactions between the edge-localized states Lee, Hosik; Son, Young-Woo; Park, Noejung Physical Review B, Vol. 72, Issue 17 https://doi.org/10.1103/physrevb.72.174431	journal	November 2005
Electronic structure and magnetic properties of graphitic ribbons Pisani, L.; Chan, J. A.; Montanari, B. Physical Review B, Vol. 75, Issue 6 https://doi.org/10.1103/physrevb.75.064418	journal	February 2007
Nonlocal exchange effects in zigzag-edge magnetism of neutral graphene nanoribbons Jung, Jeil Physical Review B, Vol. 83, Issue 16 https://doi.org/10.1103/physrevb.83.165415	journal	April 2011
Theory of Interedge Superexchange in Zigzag Edge Magnetism Jung, J.; Pereg-Barnea, T.; MacDonald, A. H. Physical Review Letters, Vol. 102, Issue 22 https://doi.org/10.1103/physrevlett.102.227205	journal	June 2009
Applicability of the Strongly Constrained and Appropriately Normed Density Functional to Transition-Metal Magnetism Fu, Yuhao; Singh, David J. Physical Review Letters, Vol. 121, Issue 20 https://doi.org/10.1103/physrevlett.121.207201	journal	November 2018
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/physrevlett.77.3865	journal	October 1996
Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N. Physical Review Letters, Vol. 91, Issue 14 https://doi.org/10.1103/physrevlett.91.146401	journal	September 2003
The electronic properties of graphene Castro Neto, A. H.; Guinea, F.; Peres, N. M. R. Reviews of Modern Physics, Vol. 81, Issue 1, p. 109-162 https://doi.org/10.1103/revmodphys.81.109	journal	January 2009
XSEDE: Accelerating Scientific Discovery Towns, John; Cockerill, Timothy; Dahan, Maytal Computing in Science & Engineering, Vol. 16, Issue 5 https://doi.org/10.1109/mcse.2014.80	journal	September 2014
Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors Calle-Vallejo, F.; Tymoczko, J.; Colic, V. Science, Vol. 350, Issue 6257 https://doi.org/10.1126/science.aab3501	journal	October 2015
Peculiar Localized State at Zigzag Graphite Edge Fujita, Mitsutaka; Wakabayashi, Katsunori; Nakada, Kyoko Journal of the Physical Society of Japan, Vol. 65, Issue 7 https://doi.org/10.1143/jpsj.65.1920	journal	July 1996
Trends in the Exchange Current for Hydrogen Evolution Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1856988	journal	January 2005

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Revisiting the link between magnetic properties and chemisorption at graphene nanoribbon zigzag edge

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