Understanding the acceleration effect of manganese and cerium doping on the hydration of CaO in CaO/Ca(OH)2 heat storage by density function theory

CaO/Ca(OH) 2 heat storage system is one of the most promising candidates for large-scale thermochemical heat storage at temperature of 300–600 °C. In this work, the CaO/Ca(OH) 2 heat storage performances of the Ce- and Mn-doped CaO were investigated and the mechanisms of promoting hydration by Ce and Mn doping were determined via density functional theory (DFT) calculations. The Mn-doped CaO exhibits the higher hydration conversion than CaO and Ce-doped CaO. The structural parameters, partial density of states, electron differential densities and energy barriers during hydration stage on the CaO, Ce- and Mn-doped CaO surfaces were compared to clarify the effects of Ce and Mn on hydration of CaO. The results show the detailed hydration reaction pathways on the CaO, Ce- and Mn-doped CaO surfaces. During the H 2 O adsorption stage, H 2 O on the Ce-doped CaO surface approaches the Ca atom first, while H 2 O on the Mn-doped CaO surface approaches the O s atom first. The adsorption energy for Ce- and Mn-doped CaO are −1.612 and −0.896 eV, respectively, which are higher than that for CaO. The doping of Ce and Mn accelerates the H 2 O adsorption on the CaO surface. The Mn doping causes the 84.3 % reduction in the energy barrier for hydration of CaO and the reduction by Mn doping is larger than that by Ce doping. Thus, Mn-doped CaO exhibits the higher hydration reactivity and hydration conversion than CaO and Ce-doped CaO. The DFT calculations determined the promotion mechanism of Ce and Mn doping on the hydration of CaO in CaO/Ca(OH) 2 heat storage.