RESUMEN
Direct ethanol fuel cells (DEFCs) play an indispensable role in the cyclic utilization of carbon resources due to its high volumetric energy density, high efficiency, and environmental benign character. However, owing to the chemically stable carbon-carbon (CâC) bond of ethanol, its incomplete electrooxidation at the anode severely inhibits the energy and power density output of DEFCs. The efficiency of CâC bond cleaving on the state-of-the-art Pt or Pd catalysts is reported as low as 7.5%. Recently, tremendous efforts are devoted to this field, and some effective strategies are put forward to facilitate the cleavage of the CâC bond. It is the right time to summarize the major breakthroughs in ethanol electrooxidation reaction. In this review, some optimization strategies including constructing core-shell nanostructure with alloying effect, doping other metal atoms in Pt and Pd catalysts, engineering composite catalyst with interface synergism, introducing cascade catalytic sites, and so on, are systematically summarized. In addition, the catalytic mechanism as well as the correlations between the catalyst structure and catalytic efficiency are further discussed. Finally, the prevailing limitations and feasible improvement directions for ethanol electrooxidation are proposed.
RESUMEN
The crucial issue restricting the application of direct ethanol fuel cells (DEFCs) is the incomplete and sluggish electrooxidation of ethanol due to the chemically stable C-C bond thereof. Herein, a unique ethylene-mediated pathway with a 100 % C1-selectivity for ethanol oxidation reaction (EOR) is proposed for the first time based on a well-structured Pt/Al2 O3 @TiAl catalyst with cascade active sites. The electrochemical in situ Fourier transform infrared spectroscopy (FTIR) and differential electrochemical mass spectrometry (DEMS) analysis disclose that ethanol is primarily dehydrated on the surface of Al2 O3 @TiAl and the derived ethylene is further oxidized completely on nanostructured Pt. X-ray absorption and density functional theory (DFT) studies disclose the Al component doped in Pt nanocrystals can promote the EOR kinetics by lowering the reaction energy barriers and eliminating the poisonous species. Strikingly, Pt/Al2 O3 @TiAl exhibits a specific activity of 3.83â mA cm-2 Pt , 7.4 times higher than that of commercial Pt/C and superior long-term durability.
RESUMEN
Porous coordination polymers have received intensive attention for pollution abatement, such as dye removal, because of their high porosity and specific surface areas. However, the commonly used water-stable porous coordination polymers are microporous and synthesized within organic solvents, which deters seriously their widespread application. In this report, we developed a facile strategy for the synthesis of mesoporous Zr-based coordination polymer (Zr-BDC-CP) within aqueous solutions. The morphology and structure of Zr-BDC-CP were characterized with scanning electron microscopy, powder X-ray diffraction, and Fourier transform infrared spectroscopy. Pore size distribution analysis confirms that the as-synthesized material is mesoporous, which allows the efficient adsorption of methylene blue, 2.6 times higher than that of the microporous coordination polymer, UiO-66. The decolorization ratio can reach higher than 93.5% in the range of 10 and 400 mg/L for methylene blue solutions. This Zr-based coordination polymer shows wonderful pH stability, where no significant loss of adsorption capacities was observed between pH values of 3 and 11. The simulation of adsorption isotherm indicates that the Freundlich model can fit the adsorption isotherm very well, which reflects that the surface of adsorbents is inhomogeneous. Fitting of kinetic curves shows that the dye adsorption by Zr-BDC-CP follows the pseudo-second-order model, which confirms that the rate-determining step may be a chemisorption process involving valence forces because of the defects within the frameworks of the mesoporous coordination polymer. Zr-BDC-CP also shows desirable recyclability without significant capacity loss. This work presents a facile and sustainable method for the preparation of mesoporous Zr-based coordination polymer for dye removal with excellent stability and recyclability, which could further push the porous coordination polymers for application in the areas of pollution abatement.