Soft
carbon is attracting tremendous attention as a promising anode
material for potassium-ion batteries (PIBs) because of its graphitizable
structure and adjustable interlayer distance. Herein, nitrogen/sulfur
dual-doped porous soft carbon nanosheets (NSC) have been prepared
with coal tar pitch as carbon precursors in an appropriate molten
salt medium. The molten salt medium and N/S dual-doping are responsible
for the formation of nanosheet-like morphology, abundant microporous
channels with a high surface area of 436 m2 g–1, expanded interlamellar spacing of 0.378 nm, and enormous defect-induced
active sites. These structural features are crucial for boosting potassium-ion
storage performance, endowing the NSC to deliver a high potassiation
storage capacity of 359 mAh g–1 at 100 mA g–1 and 115 mAh g–1 at 5.0 A g–1, and retaining 92.4% capacity retention at 1.0 A
g–1 after 1000 cycles. More importantly, the pre-intercalation
of K atom from the molten salts helps improve the initial Coulombic
efficiency to 50%, which outperforms those of the recently reported
carbon anode materials with large surface areas. The density functional
theory calculations further illuminate that the N/S dual-doping can
facilitate the adsorption of K-ion in carbon materials and decrease
the ion diffusion energy barrier during the solid-state charge migration.
Measurements of the water proton spin-lattice relaxation rate for aqueous solutions of the palindromic dodecamer, d(CGCGAATTCGCG)2, are reported as a function of the magnetic field strength. The magnitude of the relaxation rates at low magnetic field strengths and the shape of the relaxation dispersion curve permit assessment of the number of water molecules which may be considered bound to the DNA for a time equal to or longer than the rotational correlation time of the duplex. The data are examined using limiting models that arbitrarily use the measured rotational correlation time of the polynucleotide complex as a reference point for the water molecule lifetime. If it is assumed that water molecules are bound at DNA sites for times as long as or longer than the rotational correlation time of the duplex, then the magnitude of the relaxation rates at low field require that there may be only two or three such water sites. However, if the lifetime constraint is relaxed, and we assume that the number of water molecules bound to the DNA is more nearly the number identified in the X-ray structures, then the average water molecule lifetime is on the order of 1 ns. Measurements of 1H NOESY spectra demonstrate that some water molecules must have lifetimes sufficiently long that negative Overhauser effects are observed. Taken together, these results suggest a distribution of water molecule lifetimes in which most of the DNA-bound water molecule lifetimes are shorter than the rotational correlation time of the duplex, but where some have lifetimes of at least 1 ns under these concentrated conditions.
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