Probing surface defects of ZnO using formaldehyde

The catalytic properties of metal oxides are often enabled by surface defects, and their characterization is thus vital to the understanding and application of metal oxide catalysts. Typically, surface defects for metal oxides show fingerprints in spectroscopic characterization. However, we found that synchrotron-radiation photoelectron spectroscopy (SRPES) is difficult to probe surface defects of ZnO. Meanwhile, CO as a probe molecule cannot be used properly to identify surface defect sites on ZnO in infrared (IR) spectroscopy. Instead, we found that formaldehyde could serve as a probe molecule, which is sensitive to surface defect sites and could titrate surface oxygen vacancies on ZnO, as evidenced in both SRPES and IR characterization. Density functional theory calculations revealed that formaldehyde dissociates to form formate species on the stoichiometric ZnO(101¯0) surface, while it dissociates to formyl species on Vo sites of the reduced ZnO(101¯0) surface instead. Furthermore, the mechanism of formaldehyde dehydrogenation on ZnO surfaces was also elucidated, while the generated hydrogen atoms are found to be stored in ZnO bulk from 423 K to 773 K, making ZnO an interesting (de)hydrogenation catalyst.