Hydrogen Bond between Molybdate and Glucose for the Formation of Carbon-Loaded MoS₂ Nanocomposites with High...

The effects of glucose on the growth and surface properties of MoS₂ with a nanosheet structure were investigated in detail. In the presence of glucose, the hydrothermal reaction of sodium molybdate and thiourea yields carbon-loaded MoS₂ nanocomposites (C/MoS₂). Compared with bare MoS₂ nanosheets with more than six layers obtained in the absence of glucose and carbon spheres with a diameter of 500 nm prepared from the carbonization of glucose, C/MoS₂ consists of one- or three-layered MoS₂ and carbon spheres with a diameter less than 1 nm to give a large Brunauer-Emmett-Teller surface area (3-20 times larger than the individual materials). The surface characterizations reveal that both MoS₂ and carbon spheres of C/MoS₂ have a negative charge on the surface, suggesting that the previously reported explanation, in which the adsorption of MoS₂ and/or molybdate ions on carbon spheres inhibits the growth and aggregation of MoS₂, is not correct. Based on Fourier transform infrared and ¹H NMR spectra, it is demonstrated that glucose acts as the hydrogen bond donor toward polyoxomolybdate species such as Mo₈O₂₆^4-, Mo₇O₂₄^6-, and MoO₄^2- in the range of pH = 2-12. The intermolecular hydrogen bond not only inhibits the growth of both the (002) plane of MoS₂ and carbon spheres, but also enables the formation of C-O-Mo bonds in the in situ generated C/MoS₂. Compared with bare MoS₂, C/MoS₂ not only show a lower over-potential by 60 mV for the electrocatalytic evolution of hydrogen, but also has a larger mass specific capacitance by three times, due to the larger surface area and the interfacial interaction through the C-O-Mo bonds.