First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2
Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansion (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1033821
- Report Number(s):
- PNNL-SA-81153; 33194; BM0102070; TRN: US201203%%100
- Journal Information:
- Journal of Physical Chemistry C, Vol. 116, Issue 2; ISSN 1932-7447
- Country of Publication:
- United States
- Language:
- English
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