Crystallographic Visualization of a Double Water Molecule Addition on a Pt1‐MOF during the Low‐temperature Water‐Gas Shift Reaction

Abstract The low‐temperature water‐gas shift reaction (WGSR, CO+H 2 O ⇔ H 2 +CO 2 ) is considered a very promising reaction ‐candidate for fuel cells‐ despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt 1 ) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H 2 O molecule to CO, with generation of CO 2 and H 2 . Here we show, experimentally, that not one but two H 2 O molecules are added to CO on the Pt 1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in‐operando single crystal X‐ray diffraction on a Pt 1 ‐MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H 2 O molecules are recurrently added during the WGSR, not only for Pt 1 catalysts but also for other metal catalysts.