New approach to understanding the experimental Cs NMR chemical shift of clay minerals via machine learning and DFT-GIPAW calculations

Okubo, Takahiro*; Takei, Akihiro*; Tachi, Yukio; Fukatsu, Yuta; Deguchi, Kenzo*; Oki, Shinobu*; Shimizu, Tadashi*

Journal of Physical Chemistry A, 127(4), p.973 - 986, 2023/02

https://doi.org/10.1021/acs.jpca.2c08880

The identification of adsorption sites of Cs on clay minerals has been studied in the fields of environmental chemistry. The nuclear magnetic resonance (NMR) experiments allow direct observations of the local structures of adsorbed Cs. The NMR parameters of Cs, derived from solid-state NMR experiments, are sensitive to the local neighboring structures of adsorbed Cs. However, determining the Cs positions from NMR data alone is difficult. This paper describes an approach for identifying the expected atomic positions of Cs adsorbed on clay minerals by combining machine learning (ML) with experimentally observed chemical shifts. A linear ridge regression model for ML is constructed from the smooth overlap of atomic positions descriptor and gauge-including projector augmented wave (GIPAW) ab initio data. The Cs chemical shifts can be instantaneously calculated from the Cs positions on any clay layers using ML. The inverse analysis from the ML model can derive the atomic positions from experimentally observed chemical shifts.

Revealing the ion dynamics in LiGePS by quasi-elastic neutron scattering measurements

Hori, Satoshi*; Kanno, Ryoji*; Kwon, O.*; Kato, Yuki*; Yamada, Takeshi*; Matsuura, Masato*; Yonemura, Masao*; Kamiyama, Takashi*; Shibata, Kaoru; Kawakita, Yukinobu

Journal of Physical Chemistry C, 126(22), p.9518 - 9527, 2022/06

https://doi.org/10.1021/acs.jpcc.2c01748

Crystalline fully carboxylated polyacetylene obtained under high pressure as a Li-ion battery anode material

Wang, X.*; Tang, X.*; Zhang, P.*; Wang, Y.*; Gao, D.*; Liu, J.*; Hui, K.*; Wang, Y.*; Dong, X.*; Hattori, Takanori; et al.

Journal of Physical Chemistry Letters (Internet), 12(50), p.12055 - 12061, 2021/12

https://doi.org/10.1021/acs.jpclett.1c03734

Substituted polyacetylene is expected to improve the chemical stability, physical properties, and additional functions of the polyacetylene backbones, but its diversity is very limited. Here, by applying external pressure on solid acetylenedicarboxylic acid, we report the first crystalline poly-dicarboxylacetylene with every carbon on the trans-polyacetylene backbone bonded to a carboxyl group, which is very hard to synthesize by traditional methods. This unique structure combines the extremely high content of carbonyl groups and high conductivity of a polyacetylene backbone, which exhibits a high specific capacity and excellent cycling/rate performance as a Li-ion battery (LIB) anode. We present a completely functionalized crystalline polyacetylene and provide a high-pressure solution for the synthesis of polymeric LIB materials and other polymeric materials with a high content of active groups.

Electrochemically driven specific alkaline metal cation adsorption on a graphene interface

Yasuda, Satoshi; Tamura, Kazuhisa; Kato, Masaru*; Asaoka, Hidehito; Yagi, Ichizo*

Journal of Physical Chemistry C, 125(40), p.22154 - 22162, 2021/10

https://doi.org/10.1021/acs.jpcc.1c03322

Understanding electrochemical behavior of the alkaline metal cation-graphene interface in electrolyte is essential for understanding the fundamental electrochemical interface and development of graphene-based technologies. We report comprehensive analysis of the electrochemical behavior of both alkaline metal cations and graphene using electrochemical surface X-ray diffraction (EC-SXRD) and Raman (EC-Raman) spectroscopic techniques in which the interfacial structure of cations and the charging state and mechanical strain of the graphene can be elucidated. EC-SXRD and cyclic voltammetry demonstrated electrochemically driven specific adsorption and desorption of cations on the graphene surface involved in the dehydration and hydration process. This study provides new insight for understanding fundamental electrochemical behavior of the alkaline metal cation-graphene interface and contributes to the development of carbon-based novel applications.

Kinetic and Fourier transform infrared studies on the thermal decomposition of sodium hydride

Kawaguchi, Munemichi

Journal of Physical Chemistry C, 125(22), p.11813 - 11819, 2021/06

https://doi.org/10.1021/acs.jpcc.1c00538

Isothermal and constant heating thermogravimetry-differential thermal analysis (TG-DTA) and Fourier transform infrared spectrometer (FTIR) measurements have been performed for pre- and post-fired sodium hydride (NaH) in the temperature range of 500-700 K, respectively. Temperature dependence of NaH thermal decomposition rates obtained by the isothermal TGs showed an inflection point at around 620 K, which was caused by two kinds of hydrogen states (rapid diffusing and immobile hydrogen). In the FTIR spectra for the NaH and sodium (Na), the specific signals were observed at around 873.4, 1010.4, 1049.5 and 1125.7 cm, and the integrated values of FTIR signals for post-fired NaH at below 550K and at above 698 K were comparable to those for pre-fired NaH and Na, respectively. Those for post-fired NaH at 602-667 K were the intermediate values of the pre-fired NaH and Na, which denoted that the Na-Na bonds haven't grown sufficiently and the hydrogen coexisted in metallic Na. In order to predict the practical kinetics of NaH thermal decomposition reaction, we suggested the simple kinetics model which assumed two kinds of rapidly diffusing and immobile hydrogen states. The simulation results revealed the inflection point in temperature dependence of the thermal decomposition rates accordingly because the transition from immobile hydrogen to rapid diffusing hydrogen crosses over at around 620 K.

Neutron spin-echo studies of the structural relaxation of network liquid ZnCl at the structure factor primary peak and prepeak

Luo, P.*; Zhai, Y.*; Leao, J. B.*; Kofu, Maiko; Nakajima, Kenji; Faraone, A.*; Zhang, Y.*

Journal of Physical Chemistry Letters (Internet), 12(1), p.392 - 398, 2021/01

https://doi.org/10.1021/acs.jpclett.0c03146

Using neutron spin-echo spectroscopy, we studied the microscopic structural relaxation of a prototypical network ionic liquid ZnCl at the structure factor primary peak and prepeak. The results show that the relaxation at the primary peak is faster than the prepeak and that the activation energy is % higher. A stretched exponential relaxation is observed even at temperatures well-above the melting point . Surprisingly, the stretching exponent shows a rapid increase upon cooling, especially at the primary peak, where it changes from a stretched exponential to a simple exponential on approaching the . These results suggest that the appearance of glassy dynamics typical of the supercooled state even in the equilibrium liquid state of ZnCl as well as the difference of activation energy at the two investigated length scales are related to the formation of a network structure on cooling.

Gas barrier properties of chemical vapor-deposited graphene to oxygen imparted with sub-electronvolt kinetic energy

Ogawa, Shuichi*; Yamaguchi, Hisato*; Holby, E. F.*; Yamada, Takatoshi*; Yoshigoe, Akitaka; Takakuwa, Yuji*

Journal of Physical Chemistry Letters (Internet), 11(21), p.9159 - 9164, 2020/11

https://doi.org/10.1021/acs.jpclett.0c02112

Atomically thin layers of graphene have been proposed to protect surfaces through the direct blocking of corrosion reactants such as oxygen with low added weight. The long term efficacy of such an approach, however, is unclear due to the long-term desired protection of decades and the presence of defects in as-synthesized materials. Here, we demonstrate catalytic permeation of oxygen molecules through previously-described impermeable graphene by imparting sub-eV kinetic energy to molecules. These molecules represent a small fraction of a thermal distribution thus this exposure serves as an accelerated stress test for understanding decades-long exposures. The permeation rate of the energized molecules increased 2 orders of magnitude compared to their non-energized counterpart. Graphene maintained its relative impermeability to non-energized oxygen molecules even after the permeation of energized molecules indicating that the process is non-destructive and a fundamental property of the exposed material.

Unusual redox behavior of ruthenocene confined in the micropores of activated carbon

Itoi, Hiroyuki*; Ninomiya, Takeru*; Hasegawa, Hideyuki*; Maki, Shintaro*; Sakakibara, Akihiro*; Suzuki, Ryutaro*; Kasai, Yuto*; Iwata, Hiroyuki*; Matsumura, Daiju; Owada, Mao*; et al.

Journal of Physical Chemistry C, 124(28), p.15205 - 15215, 2020/07

https://doi.org/10.1021/acs.jpcc.0c02965

Confinement of hydrogen molecules at graphene-metal interface by electrochemical hydrogen evolution reaction

Yasuda, Satoshi; Tamura, Kazuhisa; Terasawa, Tomoo; Yano, Masahiro; Nakajima, Hideaki*; Morimoto, Takahiro*; Okazaki, Toshiya*; Agari, Ryushi*; Takahashi, Yasufumi*; Kato, Masaru*; et al.

Journal of Physical Chemistry C, 124(9), p.5300 - 5307, 2020/03

https://doi.org/10.1021/acs.jpcc.0c00995

Confinement of hydrogen molecules at graphene-substrate interface has presented significant importance from the viewpoints of development of fundamental understanding of two-dimensional material interface and energy storage system. In this study, we investigate H confinement at a graphene-Au interface by combining selective proton permeability of graphene and the electrochemical hydrogen evolution reaction (electrochemical HER) method. After HER on a graphene/Au electrode in protonic acidic solution, scanning tunneling microscopy finds that H nanobubble structures can be produced between graphene and the Au surface. Strain analysis by Raman spectroscopy also shows that atomic size roughness on the graphene/Au surface originating from the HER-induced strain relaxation of graphene plays significant role in formation of the nucleation site and H storage capacity.

Impact of stoichiometry on the mechanism and kinetics of oxidative dissolution of UO induced by HO and -irradiation

Kumagai, Yuta; Fidalgo, A. B.*; Jonsson, M.*

Journal of Physical Chemistry C, 123(15), p.9919 - 9925, 2019/04

https://doi.org/10.1021/acs.jpcc.9b00862

Radiation-induced oxidative dissolution of uranium dioxide (UO) is one of the most important chemical processes of U driven by redox reactions. We have examined the effect of UO stoichiometry on the oxidative dissolution of UO induced by hydrogen peroxide (HO) and -ray irradiation. By comparing the reaction kinetics of HO between stoichiometric UO and hyper-stoichiometric UO, we observed a significant difference in reaction speed and U dissolution kinetics. The stoichiometric UO reacted with HO much faster than the hyper-stoichiometric UO. The U dissolution from UO was initially much lower than that from UO, but gradually increased as the oxidation by HO proceeded. The -ray irradiation induced the U dissolution that is analogous to the kinetics by the exposure to a low concentration (0.2 mM) of HO. The exposure to higher HO concentrations caused lower U dissolution and resulted in deviation from the U dissolution behavior by -ray irradiation.