Tuning the charge states of CrW2O9 clusters deposited on perfect and defective MgO(001) surfaces with different color centers: A comprehensive DFT study

The structures and electronic properties of bimetallic oxide CrW2O9 clusters supported on the perfect and defective MgO(001) surfaces with three different color centers, FS (0), FS (+), and FS (2+) centers, respectively, have been investigated by density functional theory calculations. Our results show that the configurations, adsorption energies, charge transfers, and bonding modes of dispersed CrW2O9 clusters are sensitive to the charge states of the FS centers. Compared with the gas-phase configuration, the CrW2O9 clusters supported on the defective surfaces are distorted dramatically, which exhibit different chain structures. On the perfect MgO surface, the depositions of clusters do not involve obvious charge transfer, while the situation is quite different on the defective MgO(001) surfaces in which significant electron transfer occurs from the surface to the cluster. Interestingly, this effect becomes more remarkable for electron-rich oxygen vacancies (FS (0) center) than that for electron-poor oxygen vacancies (FS (+) and FS (2+) centers). Furthermore, our work reveals a progressive Brønsted acid sites where spin density preferentially localized around the Cr atoms not the W atoms for all kinds of FS-centers, indicating the better catalytic activities can be expected for CrW2O9 cluster on defective MgO(001) surfaces with respect to the W3O9 cluster.