Adsorption and dehydration of ethanol on isomorphously B, Al, and Ga substituted H-ZSM-5 zeolite: an embedded ONIOM study.

Dehydration reactions are important in the petroleum and petrochemical industries, especially for the feedstock production. In this work, the catalytic activity of zeolites with different acidities for the dehydration of ethanol to ethylene and diethylether is investigated by density functional calculations on cluster models of three isomorphous B, Al, and Ga substituted H-ZSM-5 zeolites. Both unimolecular and bimolecular mechanisms are investigated. Detailed reaction profiles for the dehydration reaction, assuming either a stepwise or a concerted mechanism, were calculated by using the ONIOM(MP2:M06-2X) + SCREEP method. The adsorption energies of ethanol are -21.6, -28.1, and -27.7 kcal mol-1 on H-[B]-ZSM-5, H-[Al]-ZSM-5, and H-[Ga]-ZSM-5 zeolites, respectively. The activation energies for the rate-determining step of the unimolecular concerted mechanism for the ethylene formation are 48.5, 42.6, and 43.6 kcal mol-1 on H-[B]-ZSM-5, H-[Al]-ZSM-5, and H-[Ga]-ZSM-5 zeolites, respectively. The activation energies for the ethoxy formation as the rate-determining step for the bimolecular formation of diethylether are 42.3, 40.0, and 41.1 kcal mol-1 on H-[B]-ZSM-5, H-[Al]-ZSM-5, and H-[Ga]-ZSM-5 zeolites, respectively. The results indicate that the catalytic activities for the dehydration of ethanol decrease in the order H-[Al]-ZSM-5 ~ H-[Ga]-ZSM-5 > H-[B]-ZSM-5. Besides the acid strength, the zeolite framework affects the reaction by stabilizing the reaction intermediates, leading to more stable adsorption complexes and lower activation barriers.

Alpha-MnO2 nanofibers/nitrogen and sulfur-co-doped reduced graphene oxide for 4.5 V quasi-solid state supercapacitors using ionic liquid-based polymer electrolyte.

α-MnO2 nanofibers combined with nitrogen and sulfur co-doped reduced graphene oxide (α-MnO2/N&S-rGO) were prepared through simple hydrothermal and ball milling processes. Structural characterization results by X-ray diffraction, X-ray photoemission spectroscopy, electron microscopy and Raman spectroscopy demonstrated that α-MnO2 nanofibers with the average diameter of ~40 nm were well dispersed on N&S-rGO nanoflakes. The synthesized material was incorporated into supercapacitor (SC) electrodes and assembled with the quasi-solid-state electrolyte comprising N,N-Diethyl-N-methyl-N-(2-methoxy-ethyl)ammonium bis (trifluoromethyl-sulfonyl)amide [DEME][TFSA]/polyvinylidene fluoride-hexafluoropropylene (PVDF-co-HFP) to produce coin-cell SCs. Electrochemical performances of SCs were measured by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. From the electrochemical data, SC using α-MnO2/N&S-rGO exhibited a good specific capacitance of 165F g-1 at 0.25 A g-1 with a wide potential window of 0-4.5 V, corresponding to a high energy density of 110 Wh kg-1 and a power density of 550 W kg-1. In addition, it exhibited good electrochemical stability with a capacitance retention of 75% after 10,000 cycles at 1 A g-1 and a low self-discharge loss. The attained energy-storage performances indicated that the α-MnO2/N&S-rGO composite could be highly promising for high-performance ionic liquid-based quasi solid-state supercapacitors.