This report describes a dehydration of fructose into 5-hydroxymethylfurfural (HMF) promoted by ionic liquids [Bmim]Cl and [HNMP][CH 3 SO 3 ] in ethanol solvent. Two intermediates captured in time-dependent HPLC determinations are identified and structurally characterized by in situ 1 H NMR and online ESI(+)-MS/MS. Studies on the influence of the ionic liquids (ILs) on the formation and transformation of the intermediates indicate that [HNMP]-[CH 3 SO 3 ] promotes the formation of the intermediates, while [Bmim]Cl promotes their transformation. The contribution of the component ions of the ILs to the dehydration originates from their activation toward the leaving of OH on fructose or the intermediates via the formation of multiple hydrogen bonds. This kind of weak interaction appears only at low temperature. On the basis of the present study and the related literature, we propose a concerted mechanism for the binary IL-promoted conversion of fructose into HMF at room temperature.
By selectively dealloying a PtCoAl ternary alloy, a novel nanoporous PtCo (np-PtCo) alloy with a three-dimensional bicontinuous pore-ligament structure is successfully fabricated. X-ray diffraction and electron microscopic characterizations demonstrate the single-crystal nature of the alloy ligament with a ligament size down to ~3 nm. After a mild electrochemical dealloying process, a nanoporous near-surface alloy structure with a Pt-rich surface and a PtCo alloy core is obtained. Electrochemical measurements show that the np-PtCo surface alloy has greatly enhanced catalytic activity and durability toward methanol electrooxidation compared with a state-of-the-art Pt/C catalyst. The peak current density of methanol electrooxidation on a np-PtCo surface alloy is more than 5 times of that on Pt/C. More importantly, continuous potential cycling from 0.6 to 0.9 V (vs RHE) in a 0.5 M H(2)SO(4) aqueous solution demonstrates that a np-PtCo surface alloy has excellent structure stability, with more than 90% of the initial electrochemical active surface area (EASA) retained after 5000 potential cycles. Under the same conditions, the EASA of Pt/C drops to ~70%. With evident advantages of facile preparation as well as enhanced electrocatalytic activity and durability, a np-PtCo surface alloy nanomaterial holds great potential as an anode catalyst in direct methanol fuel cells.
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