Unveiling the Role and Stabilization Mechanism of Cu<sup>+</sup> into Defective Ce-MOF Clusters during CO Oxidation
Sergio Rojas‐Buzo, Davide Salusso, Thanh-Hiep Thi Le, Manuel Á. Ortuño, Kirill A. Lomachenko, Silvia Bordiga
Abstract
High Resolution Image Download MS PowerPoint Slide Copper single-site catalysts supported on Zr-based metal–organic frameworks (MOFs) are well-known systems in which the nature of the active sites has been deeply investigated. Conversely, the redox chemistry of the Ce-counterparts is more limited, because of the often-unclear Cu 2+ /Cu + and Ce 4+ /Ce 3+ pairs behavior. Herein, we studied a novel Cu 2+ single-site catalyst supported on a defective Ce-MOF, Cu/UiO-67(Ce), as a catalyst for the CO oxidation reaction. Based on a combination of in situ DRIFT and operando XAS spectroscopies, we established that Cu + sites generated during catalysis play a pivotal role. Moreover, the oxygen vacancies associated with Ce 3+ sites and presented in the defective Cu/UiO-67(Ce) material are able to activate the O 2 molecules, closing the catalytic cycle. The results presented in this work open a new route for the design of active and stable single-site catalysts supported on defective Ce-MOFs.