Predictive screening and validation on chemical looping oxygen carrier activation by tuning electronic structures via transition metal dopants

Owing to its high fuel conversion efficiency and in-situ CO2 capture capability, chemical looping is a promising and versatile platform for fossil fuel utilization. Through the circulation of oxygen carriers (OCs), which are usually metal oxides, the carbonaceous fuels are oxidized into power/heat and/or value-added chemicals by lattice oxygen of OC in the fuel reactor. The reactivity of OC towards the carbonaceous fuels is crucial to the success of chemical looping processes. Incorporating low-percentage dopants into OC is a promising strategy to improve their reactivity while maintaining the recyclability. Consequently, a systematic screening strategy in dopant selection with a solid physical foundation is highly desired. Using hematite (alpha-Fe2O3) as the model OC material, density functional theory calculations were conducted herein to exemplify the impact of transition metal dopants on the surface reactivity with CO and CH4, the two most common C1 reducing agents in fossil fuels. We found that the amount of electrons accumulated on the lattice oxygen that bound with dopants is a key descriptor to evaluating the surface reactivity in the Mars-van Krevelen type reactions, which can be tailored by dopants with different electronegativities. Cu and Ni were predicted to be the most effective dopants, and such theoretical predictions were validated in temperature-programmed reduction and cyclic redox experiments, where a significant reactivity enhancement was observed using only 1% atomic ratio of effective dopants. The proposed screening strategy is expected to facilitate new OC designs and modifications in an energy and cost effective manner, thus significantly expedites the development of chemical looping technologies.