Calorimetric and spectroscopic studies on solvation energetics for H₂ storage in the CO₂/HCOOH system

Physical Chemistry Chemical Physics : PCCP
Cornel FinkGábor Laurenczy

Abstract

Solvents playing a crucial role in many chemical reactions and additives can be used to shift the reaction equilibrium. Herein we study the enthalpy of mixing for selected solvents (aqueous, organic) and basic additives (amines, aqueous KOH) when mixed with formic acid with the aim to optimize hydrogen storage/delivery in the CO2/HCOOH system. Formic acid, resulting from carbon dioxide hydrogenation, reaches highest yields when effectively "removed" from the reaction equilibrium. In terms of energy efficiency, any heat released during CO2 hydrogenation has to be reused in the reverse reaction, during the production of hydrogen. In any scenario, the usage of basic chemicals, non-innocent solvents, causes higher energy release in CO2 hydrogenation, which has to be reused in the hydrogen delivery process. Therefore, the enthalpy of mixing is a valuable parameter for designing hydrogen storage devices since it allows the estimation of energy balance for the CO2 hydrogenation/H2 liberation cycle. The highest formic acid concentrations in direct catalytic CO2 hydrogenation under acidic conditions were reached in DMSO. DMSO exhibits considerably stronger interactions with formic acid compared to water as was observed in calorimetric m...Continue Reading

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Citations

Jun 27, 2017·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Lin WangYuichiro Himeda
Jun 8, 2018·Chemistry : a European Journal·Eric S Wiedner, John C Linehan
Jul 13, 2018·ChemSusChem·Cecilia MondelliJavier Pérez-Ramírez
Jan 18, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Cornel Fink, Gábor Laurenczy
Oct 7, 2017·Chemical Reviews·Katerina SordakisGábor Laurenczy
Dec 22, 2021·Physical Chemistry Chemical Physics : PCCP·Yang CongHui Li

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