TY - JOUR
T1 - Competition between Hydrogen Bonding and Dispersion Force in Water Adsorption and Epoxy Adhesion to Boron Nitride
T2 - From the Flat to the Curved
AU - Tsuji, Yuta
AU - Yoshizawa, Kazunari
N1 - Funding Information:
This work was supported by KAKENHI grants (numbers JP17K14440, JP17H03117, and JP21K04996) from the Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) through the MEXT projects Integrated Research Consortium on Chemical Sciences, Cooperative Research Program of Network Joint Research Center for Materials and Devices and Elements Strategy Initiative to Form Core Research Center, and by JST-CREST JPMJCR15P5, and JST-Mirai JPMJMI18A2. The computations in this work were primarily performed using the computer facilities at the Research Institute for Information Technology, Kyushu University. Y.T. is grateful for a JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Discrete Geometric Analysis for Materials Design, grant number JP20H04643, and Mixed Anion, grant number JP19H04700).
Publisher Copyright:
© 2021 American Chemical Society
PY - 2021/9/28
Y1 - 2021/9/28
N2 - Hexagonal boron nitride (h-BN) is a material with excellent thermal conductivity and electrical insulation, used as an additive to various matrices. To increase the affinity of h-BN to them, hydrogen bonds should be formed at the interface. In reality, however, they are not formed; the N atoms are not capable of accepting hydrogen bonds due to the delocalization of their lone pair electrons over the B-N π bonds. To make it form hydrogen bonds, one may need to break the planarity of h-BN so that the orbital overlap in the B-N π bonds can be reduced. This idea is verified with first-principles calculations on the adsorption of a water molecule on hypothetical h-BN surfaces, the planarity of which is broken. One can do it in silico but not in vitro. BN nanotubes (BNNTs) are considered as a more realistic BN surface with nonplanarity. The hydrogen bond is shown to become stronger as the curvature of the tube increases. On the contrary, the strength of the dispersion force acting at the interface becomes weaker. In water adsorption, these two interactions are in competition with each other. However, in epoxy adhesion, the interaction due to dispersion forces is overwhelmingly stronger than that due to hydrogen bonding. The smaller the curvature of the surface, the smaller the distance between more atoms at the interface; thus, the interaction due to dispersion forces maximized.
AB - Hexagonal boron nitride (h-BN) is a material with excellent thermal conductivity and electrical insulation, used as an additive to various matrices. To increase the affinity of h-BN to them, hydrogen bonds should be formed at the interface. In reality, however, they are not formed; the N atoms are not capable of accepting hydrogen bonds due to the delocalization of their lone pair electrons over the B-N π bonds. To make it form hydrogen bonds, one may need to break the planarity of h-BN so that the orbital overlap in the B-N π bonds can be reduced. This idea is verified with first-principles calculations on the adsorption of a water molecule on hypothetical h-BN surfaces, the planarity of which is broken. One can do it in silico but not in vitro. BN nanotubes (BNNTs) are considered as a more realistic BN surface with nonplanarity. The hydrogen bond is shown to become stronger as the curvature of the tube increases. On the contrary, the strength of the dispersion force acting at the interface becomes weaker. In water adsorption, these two interactions are in competition with each other. However, in epoxy adhesion, the interaction due to dispersion forces is overwhelmingly stronger than that due to hydrogen bonding. The smaller the curvature of the surface, the smaller the distance between more atoms at the interface; thus, the interaction due to dispersion forces maximized.
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U2 - 10.1021/acs.langmuir.1c01935
DO - 10.1021/acs.langmuir.1c01935
M3 - Article
C2 - 34519515
AN - SCOPUS:85115781368
VL - 37
SP - 11351
EP - 11364
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 38
ER -