Structure and properties of KNi–hexacyanoferrate Prussian Blue Analogues for efficient CO2 capture: Host–guest interaction chemistry and dynamics of CO2 adsorption

Abstract

Potassium Nickel hexacyanoferrate Prussian Blue Analogues (K-NiFe-PBAs) offer an excellent platform for efficient CO2 capture due to their porous nature and accessible channels. Herein, the effect of Ni:K atomic ratio on the structure and the CO2 storage capacity was studied by employing K-NiFe-PBAs with Ni:K ratio of ca. 2.5 and 12. The porosity and the isosteric heat of CO2 adsorption can be modulated and optimized by varying the Ni:K atomic ratio in the PB framework and thus, covering the thermodynamic criterion for easy CO2capture and release with acceptable energy costs. The synthesized K-NiFe-PBAs containing only trace amounts of K+ ions (with Ni:K = 12) shows an adsorption capacity (∼3.0 mmol g–1 CO2 at 273 K and 100 kPa) comparable to other well established CO2 adsorbents. In situ FTIR spectroscopy was further employed to elucidate the host–guest interaction chemistry and the dynamics of K-NiFe-PBAs within CO2 and H2O. The analysis enabled, to the best of our knowledge, is the first FTIR spectroscopic observation of the high sensitivity of the material to structural distortions induced by small changes under water vapor pressure. It was found that H2O hardly affects CO2 adsorption and the materials are perspective for CO2 capture in the presence of water.