Revealing the mechanism of oxygen vacancy defect for CO2 adsorption and diffusion on CaO: DFT and experimental study

The calcium looping is a promising technology to achieve industrial CO2 capture, and the introduction of oxygen vacancy can promote the CO2 capture reactivity of CaO-based sorbents. In this work, DFT calculations were performed to investigate the CO2 adsorption by CaO in the presence of oxygen vacancy defect. The presence of oxygen vacancy reduces the band gap of CaO surface, which results from the delocalization of Ca 2p orbital. Besides, the electron accumulation at the oxygen vacancy occurs due to the unsaturated Ca-O bonds, and the reaction possibility is promoted neighbouring the defect. The top site of oxygen vacancy defect of CaO is favourable for CO2 adsorption. The adsorption energy of CO2 on CaO with oxygen vacancy achieves − 2.52 eV, which is 1.81 times as high as that on pristine CaO. Due to strong interaction between CO2 and CaO with oxygen vacancy, CO2 migration from this site is more difficult, while the following diffusion is more prone to occur. In the presence of steam, CO2 adsorption energy is enhanced to − 2.70 eV on CaO with oxygen vacancy, and the distance from CO2 radical to surface is intuitively reduced, which results from the electrons donated from defect and neighbouring Ca atoms, while CO2 diffusion difficulty is increased. This work provides an incisive investigation for structural, electronic, and thermodynamic characteristics of CO2 adsorption and diffusion on CaO in the presence of oxygen vacancy defect, and it can shed light on rational synthesis and functional design of surface-active sites of CaO-based sorbents.