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J Phys Chem Lett. 2014 Aug 7;5(15):2613-8. doi: 10.1021/jz501218f. Epub 2014 Jul 22.

Gasification Mechanism of Carbon with Supercritical Water at Very High Pressures: Effects on H2 Production.

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†Departamento Química Física, Facultad de Ciencias Químicas, Universidad de Salamanca, Plaza de la Merced s/n 37008 Salamanca, Spain.


The scarce data concerning the gasification of carbonaceous solids with supercritical water (SCW) suggest the great potential of this method to produce a valuable green fuel such as H2. However, the extraordinary properties of SCW have not been properly applied to H2 production because the mechanism that governs gasification under these conditions remains unclear. Here, we present a study in which this reaction is explored within the largest pressure range ever assayed in this field, from 1 to 1000 bar. The amplitude of the experimental conditions investigated highlights the various pathways that govern gasification with steam and SCW. Under supercritical conditions, the clusters formed around the superficial groups of the solid reduce the energetic requirements for gasification and generate CO2 as a primary product of the reaction. Consequently, gasification with SCW is significantly faster than that using steam, and the produced gases are richer and more appropriate to obtain pure H2.


cluster; hydrogen inhibition; syngas reaction; transition-state complex; water−gas shift reaction


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