TY - JOUR
T1 - Reaction Kinetics for the Covalent Functionalization of Two-Dimensional MoS 2 by Aryl Diazonium Salts
AU - Li, Duo O.
AU - Chu, Ximo S.
AU - Wang, Qing
N1 - Funding Information:
This work was supported by the NSF Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (EEC-1449500) and by NSF grant DMR-1610153. We gratefully acknowledge Prof. Candace Chan for helpful discussions, and Prof. Hao Yan for use of the AFM and Raman systems.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/4/30
Y1 - 2019/4/30
N2 - The two-dimensional transition-metal dichalcogenide molybdenum disulfide (MoS 2 ) has been intensely studied in the past several years due to its exceptional electronic, optical, and chemical properties in a wide range of applications. The chemical functionalization of MoS 2 allows its properties and interfacial interactions to be tuned and controlled. Recently, we reported the direct covalent functionalization of semiconducting MoS 2 with aryl diazonium salts, without the use of harsh initial treatments or phase engineering. In this paper, we confirm and expand the covalent functionalization reaction model by performing a detailed study of the reaction kinetics for monolayer MoS 2 functionalized by 4-nitrobenzene tetrafluoroborate (4-NBD). We find that both the Freundlich and Temkin isotherm models are good descriptors of the reaction due to the energetically inhomogeneous surface of MoS 2 and the indirect adsorbate-adsorbate interactions from previously attached nitrophenyl groups, respectively. The reaction kinetics was then found to be well described using a pseudo-second-order model, showing that the order of this reaction is two. This study supports our previous work and gives us a deeper understanding of the nature of the covalent functionalization of MoS 2 .
AB - The two-dimensional transition-metal dichalcogenide molybdenum disulfide (MoS 2 ) has been intensely studied in the past several years due to its exceptional electronic, optical, and chemical properties in a wide range of applications. The chemical functionalization of MoS 2 allows its properties and interfacial interactions to be tuned and controlled. Recently, we reported the direct covalent functionalization of semiconducting MoS 2 with aryl diazonium salts, without the use of harsh initial treatments or phase engineering. In this paper, we confirm and expand the covalent functionalization reaction model by performing a detailed study of the reaction kinetics for monolayer MoS 2 functionalized by 4-nitrobenzene tetrafluoroborate (4-NBD). We find that both the Freundlich and Temkin isotherm models are good descriptors of the reaction due to the energetically inhomogeneous surface of MoS 2 and the indirect adsorbate-adsorbate interactions from previously attached nitrophenyl groups, respectively. The reaction kinetics was then found to be well described using a pseudo-second-order model, showing that the order of this reaction is two. This study supports our previous work and gives us a deeper understanding of the nature of the covalent functionalization of MoS 2 .
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U2 - 10.1021/acs.langmuir.8b04288
DO - 10.1021/acs.langmuir.8b04288
M3 - Article
C2 - 30950619
AN - SCOPUS:85065011316
VL - 35
SP - 5693
EP - 5701
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 17
ER -