Endergonic Hydrogenation at Ambient Conditions Using an Electrochemical Membrane Reactor.

Here, we determine how the hydrogen loading ( x ) of an electrochemical palladium membrane reactor (ePMR) varies with electrochemical conditions (e.g., applied current density, electrolyte concentration). We detail how x influences the thermodynamic driving force of an ePMR. These studies are accomplished by measuring the fugacity ( P ) of hydrogen desorbing from the palladium-hydrogen membrane and subsequently relating P to pressure-composition isotherms to determine x . We find that x increases with both applied current density and electrolyte concentration, but plateaus at a loading of x ≅ 0.92 in 1.0 M H 2 SO 4 at -200 mA·cm -2 . The validity of the fugacity measurements is supported experimentally and computationally by: (a) electrochemical hydrogen permeation studies; and (b) a palladium-hydrogen porous flow finite element analysis (FEA) model. Both (a) and (b) agree with the fugacity measurements on the following x -dependent properties of the palladium-hydrogen system during electrolysis: (i) the onset for spontaneous hydrogen desorption; (ii) the point of steady-state hydrogen loading; and (iii) the function describing hydrogen desorption between (i) and (ii). We proceed to detail how x defines the free energy of palladium-hydrogen alloy formation (Δ G ( x ) PdH ), which is a descriptor for the thermodynamic driving force of hydrogenation at the PdH x surface of an ePMR. A maximum value Δ G PdH of 11 kJ·mol -1 is observed, suggesting that an ePMR is capable of driving endergonic hydrogenation reactions. We empirically demonstrate this capability by reducing carbon dioxide to formate (Δ G CO 2 /HCO 2 H = 3.4 kJ·mol -1 ) at ambient conditions and neutral pH.