TY - JOUR
T1 - Extensive first-principles molecular dynamics study on Li encapsulation into C60 and its experimental confirmation
AU - Ohno, K.
AU - Manjanath, A.
AU - Kawazoe, Yoshiyuki
AU - Hatakeyama, R.
AU - Misaizu, F.
AU - Kwon, E.
AU - Fukumura, Hiroshi
AU - Ogasawara, H.
AU - Yamada, Y.
AU - Zhang, C.
AU - Sumi, N.
AU - Kamigaki, T.
AU - Kawachi, K.
AU - Yokoo, K.
AU - Ono, S.
AU - Kasama, Y.
N1 - Funding Information:
We are very grateful to Prof. Tsutomu Ohtsuki at Kyoto University, Prof. Ken Kokubo at Osaka University, and Prof. Jun Onoe and Prof. Masato Nakaya at Nagoya University, for a lot of helpful discussion. We also thank Ms. Kaori Yokota for helping us perform error estimation using neural networks. This study was supported by the New Energy and Industrial Technology Development Organization (NEDO); the project name is “Investigation of Technological Development of New Nanocarbon Materials in collaboration of first-principles calculations and experiments” (No. 16101402-0). We are also indebted to the HPCI project promoted by the Research Organization for Information Science and Technology (RIST) and supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) for the use of the supercomputer SR16000 at Hokkaido University and at IMR, Tohoku University (Project IDs. hp160072, hp160234, hp170268, and hp170190). This work was also partially supported by the “Center for Fundamental and Applied Research of Novel Nanocarbon Derivatives (FARNND), Center for Key Interdisciplinary Research”, and “Creation of International Research Center for Atom-Endohedral Fullerene Nanobiotronics, Program for Key Interdisciplinary Research”, Tohoku University, in Japan.
Publisher Copyright:
© The Royal Society of Chemistry 2018.
PY - 2018/1/28
Y1 - 2018/1/28
N2 - The aim of increasing the production ratio of endohedral C60 by impinging foreign atoms against C60 is a crucial matter of the science and technology employed towards industrialization of these functional building block materials. Among these endohedral fullerenes, Li+@C60 exhibits a wide variety of physical and chemical phenomena and has the potential to be applicable in areas spanning the medical field to photovoltaics. However, currently, Li+@C60 can be experimentally produced with only ∼1% ratio using the plasma shower method with a 30 eV kinetic energy provided to the impinging Li+ ion. From extensive first-principles molecular dynamics simulations, it is found that the maximum production ratio of Li+@C60 per hit is increased to about 5.1% (5.3%) when a Li+ ion impinges vertically on a six-membered ring of C60 with 30 eV (40 eV) kinetic energy, although many C60 molecules are damaged during this collision. On the contrary, when it impinges vertically on a six-membered ring with 10 eV kinetic energy, the production ratio remains at 1.3%, but the C60 molecules are not damaged at all. On the other hand, when the C60 is randomly oriented, the production ratio reduces to about 3.7 ± 0.5%, 3.3 ± 0.5%, and 0.2 ± 0.03% for 30 eV, 40 eV, and 10 eV kinetic energy, respectively. Based on these observations we demonstrate the possibility of increasing the production ratio by fixing six-membered rings atop C60 using the Cu(111) substrate or UV light irradiation. In order to assess the ideal experimental production ratio, the 7Li solid NMR spectroscopy measurement is also performed for the multilayer randomly oriented C60 sample irradiated by Li+ using the plasma shower method combined with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Time-of-flight mass spectroscopy measurements are also performed to cross check whether Li+@C60 molecules are produced in the sample. The resulting experimental estimate, 4% for 30 eV incident kinetic energy, fully agrees with our simulation results mentioned above, suggesting the consistency and accuracy of our simulations and experiments.
AB - The aim of increasing the production ratio of endohedral C60 by impinging foreign atoms against C60 is a crucial matter of the science and technology employed towards industrialization of these functional building block materials. Among these endohedral fullerenes, Li+@C60 exhibits a wide variety of physical and chemical phenomena and has the potential to be applicable in areas spanning the medical field to photovoltaics. However, currently, Li+@C60 can be experimentally produced with only ∼1% ratio using the plasma shower method with a 30 eV kinetic energy provided to the impinging Li+ ion. From extensive first-principles molecular dynamics simulations, it is found that the maximum production ratio of Li+@C60 per hit is increased to about 5.1% (5.3%) when a Li+ ion impinges vertically on a six-membered ring of C60 with 30 eV (40 eV) kinetic energy, although many C60 molecules are damaged during this collision. On the contrary, when it impinges vertically on a six-membered ring with 10 eV kinetic energy, the production ratio remains at 1.3%, but the C60 molecules are not damaged at all. On the other hand, when the C60 is randomly oriented, the production ratio reduces to about 3.7 ± 0.5%, 3.3 ± 0.5%, and 0.2 ± 0.03% for 30 eV, 40 eV, and 10 eV kinetic energy, respectively. Based on these observations we demonstrate the possibility of increasing the production ratio by fixing six-membered rings atop C60 using the Cu(111) substrate or UV light irradiation. In order to assess the ideal experimental production ratio, the 7Li solid NMR spectroscopy measurement is also performed for the multilayer randomly oriented C60 sample irradiated by Li+ using the plasma shower method combined with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Time-of-flight mass spectroscopy measurements are also performed to cross check whether Li+@C60 molecules are produced in the sample. The resulting experimental estimate, 4% for 30 eV incident kinetic energy, fully agrees with our simulation results mentioned above, suggesting the consistency and accuracy of our simulations and experiments.
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U2 - 10.1039/c7nr07237f
DO - 10.1039/c7nr07237f
M3 - Article
C2 - 29308793
AN - SCOPUS:85041194134
VL - 10
SP - 1825
EP - 1836
JO - Nanoscale
JF - Nanoscale
SN - 2040-3364
IS - 4
ER -