The adsorption kinetics of CO2 on copper hexacyanoferrate studied by thermogravimetric analysis

The CO2 adsorption and CO2 adsorption kinetics were evaluated by thermogravimetry on two Prussian blue analogues, K2x/3CuII [FeIIx FeIII1-x (CN)6]2/3, with nominally K-free x = 0.0 and K-rich x = 1.0. Differential isosteric heats of adsorption were determined from adsorption isotherms using the Clausius-Clapeyron equation and integral values by differential scanning calorimetry. The average differential heats of CO2 adsorption are 28 kJ/mol for x = 0.0 and 33 kJ/mol for x = 1.0. Both compositions show small maxima in differential heat at ∼1 mmol/g. The integral adsorption heats were determined to be 26 kJ/mol for both x = 0.0 and x = 1.0. The kinetic CO2 adsorption/desorption curves can be modeled by a double exponential function describing two parallel processes with different rate constants. The activation energies for CO2 adsorption on x = 0.0 were 6 (1) kJ/mol for the faster component and 16 (1) kJ/mol for the slower one, while the corresponding values for x = 1.0 were 9 (1) kJ/mol and 7 (1) kJ/mol, respectively. The maximum CO2 uptake for both compositions was found to be ∼4.5 mmol/g, 19.8 wt %, at 1 bar and 273 K. The materials exhibited fast adsorption kinetics and stable cyclic performance at room temperature. The kinetics were slower for the samples with x = 1.0 than for x = 0.0 which may be attributed to interactions between CO2 molecules and K+ ions.