Bifunctionality of Re Supported on TiO(2) in Driving Methanol Formation in Low-Temperature CO(2) Hydrogenation

[Image: see text] Low temperature and high pressure are thermodynamically more favorable conditions to achieve high conversion and high methanol selectivity in CO(2) hydrogenation. However, low-temperature activity is generally very poor due to the sluggish kinetics, and thus, designing highly selective catalysts active below 200 °C is a great challenge in CO(2)-to-methanol conversion. Recently, Re/TiO(2) has been reported as a promising catalyst. We show that Re/TiO(2) is indeed more active in continuous and high-pressure (56 and 331 bar) operations at 125–200 °C compared to an industrial Cu/ZnO/Al(2)O(3) catalyst, which suffers from the formation of methyl formate and its decomposition to carbon monoxide. At lower temperatures, precise understanding and control over the active surface intermediates are crucial to boosting conversion kinetics. This work aims at elucidating the nature of active sites and active species by means of in situ/operando X-ray absorption spectroscopy, Raman spectroscopy, ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transient operando DRIFTS studies uncover the activation of CO(2) to form active formate intermediates leading to methanol formation and also active rhenium carbonyl intermediates leading to methane over cationic Re single atoms characterized by rhenium tricarbonyl complexes. The transient techniques enable us to differentiate the active species from the spectator one on TiO(2) support, such as less reactive formate originating from spillover and methoxy from methanol adsorption. The AP-XPS supports the fact that metallic Re species act as H(2) activators, leading to H-spillover and importantly to hydrogenation of the active formate intermediate present over cationic Re species. The origin of the unique reactivity of Re/TiO(2) was suggested as the coexistence of cationic highly dispersed Re including single atoms, driving the formation of monodentate formate, and metallic Re clusters in the vicinity, activating the hydrogenation of the formate to methanol.