Active sites of atomically dispersed Pt supported on Gd-doped ceria with improved low temperature performance for CO oxidation.

"Single - atom" catalysts (SACs) have been the focus of intense research, due to debates about their reactivity and challenges toward determining and designing "single - atom" (SA) sites. To address the challenge, in this work, we designed Pt SACs supported on Gd-doped ceria (Pt/CGO), which showed improved activity for CO oxidation compared to its counterpart, Pt/ceria. The enhanced activity of Pt/CGO was associated with a new Pt SA site which appeared only in the Pt/CGO catalyst under CO pretreatment at elevated temperatures. Combined X-ray and optical spectroscopies revealed that, at this site, Pt was found to be d-electron rich and bridged with Gd-induced defects via an oxygen vacancy. As explained by density functional theory calculations, this site opened a new path via a dicarbonyl intermediate for CO oxidation with a greatly reduced energy barrier. These results provide guidance for rationally improving the catalytic properties of SA sites for oxidation reactions.

First principles insights into stability of defected MXenes in water.

Two-dimensional transition metal carbides and nitrides, known as MXenes, have demonstrated remarkable performance in electrochemical energy storage and various other applications. Despite their potential, MXenes exhibit instability in aqueous solutions, and the role of defects in their aqueous stability is unclear. In this study, we report on the interfacial chemistry between water and defected Ti3C2O2 MXene at room temperature using first principles molecular dynamics simulations. We investigate how defects such as O vacancy, Ti vacancy, F terminal groups, and Ti-O vacancy pair influence the chemical interaction of water molecules with the basal plane of Ti3C2O2. Our results show that water molecules can repair the surface O vacancies, by dissociating to hydroxide and hydronium. On the other hand, F terminal groups cannot effectively block water chemisorption on the surface Ti, while Ti vacancies behave as a spectator species on the surface with respect to interaction with water. Ti3C2O2 with a Ti-O vacancy pair is found to behave like Ti3C2O2 with an O vacancy where a water molecule dissociates and refills the vacancy. These findings enrich our understanding of water interaction with defects on the MXene surfaces.