Revealing the mechanism of hydration on the CO2 kinetic adsorption of CaO surface via ReaxFF MD simulations with experiments

Hydration has been regarded as an effective method to improve the cyclic activity of CaO during the Calcium looping CO2 capture process, but its mechanism remains unclear. In this work, the hydration reaction of CaO surface and its underlying mechanism was studied by ReaxFF molecular dynamics simulation combing with TGA experiments. The effect of hydration on the initial CO2 adsorption rate showed a trend of promoting at low H2O degree and inhibiting at high H2O concentration. The CaO surface was easily passivated, and it can maintain its crystal structure and begin to distort at about 1.0 H2O monolayer contents. Hydration failed to promote the CO2 adsorption rate, inversely the CO2 adsorption process accelerated the diffusion of H ions inward the CaO lattice·H2O dissociation produced two hydroxyl groups: direct OwH and indirect OsH. Atomic density profiles showed that the direct hydroxyl pairs were always, and indirect OsH groups can consume surface oxygen active sites, reducing the initial rapid CO2 adsorption activity. On the pre-hydrated CaO surface, CO2 molecules were more likely to bind to solid oxygen active sites than OH groups. The H free radical diffused inside the lattice in the form of transition HO2 state, promoting the slow CO2 adsorption amount.