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Confinement effects on the solvation structure of solvated alkaline metal cations in a single-digit 1T-MoS2 nanochannel: A first-principles study

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0047554· OSTI ID:1781759
 [1];  [2];  [1];  [3];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of California, Riverside, CA (United States)
  3. Univ. of California, Los Angeles, CA (United States)
+ Show Author Affiliations
Confinement plays an important role in determining ion transport in porous materials, which, in turn, may influence the performance of many energy storage and desalination devices. In this work, we combined density functional theory (DFT) with an implicit solvation model and ab initio molecular dynamics (AIMD) to investigate the effects of nanoconfinement on several solvated alkaline metal cations in a single-digit 1T-MoS2 nanochannel. Our DFT calculations with a solvation model indicated that cations with stronger hydration energy introduce a higher number of co-intercalated water molecules into the channel, consistent with early experimental observation obtained for MXene (2D transition metal carbide) channels. The predicted optimal water numbers for the cations were then used for AIMD simulations that explicitly include the effects of the solvent. When compared with the cations in bulk solution, our simulations showed that the hydration structure and coordination number (CN) of the solvated cations confined in the MoS2 channel can be significantly altered. Further, we found that larger cations with weaker hydration energy (K+, Rb+, and Cs+) exhibited a distinctive CN decrease under confinement, while smaller cations (Li+ and Na+) retained a similar hydration shell as in the bulk solution. More specifically, the hydration shell of large cations (K+, Rb+, and Cs+) in MoS2 showed similar features of the coordination angle to the bulk, which suggests the partially broken hydration shell with no geometry change under confinement. Our simulations provided insights into the change of the hydration structure of alkaline metal cations under confinement, which may have important implications on their transport in the 1T-MoS2 channel.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Enhanced Nanofluidic Transport (CENT); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-07NA27344; SC0019112
OSTI ID:
1781759
Report Number(s):
LLNL-JRNL--818694; 1029289
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
Ab-initio molecular dynamics
Density functional theory
Desalination
Energy storage
First-principle calculations
Implicit solvation
Nanochannels
Nanomaterials
Porous media
Reference interaction site model