Spectroscopy and Catalysis: The Operando Methodology and Reaction Monitoring, Tools to Understand Structure-Activity Relationships Miguel Banares1; Raquel Portela1; Mariví Martinez Huerta1; Pedro Avila1; Susana Pérez Ferreras1; Søren Birk Rasmussen1; Vanesa Calvino Casilda2; Alba E. Diaz Alvarez1; Ines Reyero1; Katarzyna Stawicka3; Maciej Trejda3; Maria Ziolek3; Olga Guerrero4; Marco Daturi5; Philippe Bazin5; Guillaume Clet5; Zhenyou Gui6; Nanette Zahrtmann7; Shunmugavel Saravana6; Zhiwen Qi8; Anders Riisager7; Eduardo J. García Suárez7; 1INSTITUTE FOR CATALYSIS AND PETROLEUM CHEMISTRY (CSIC), Madrid, Spain; 2ETS DE INGENIEROS INDUSTRIALES, UNED, Madrid, Spain; 3ADAM MICKIEWICZ UNIVERSITY, Poznan, Poland; 4UNIVERSITY OF MALAGA, Malaga, Spain; 5LCS UNIVERSITY OF CAEN NORMANDY, Caen, France; 6DTU CHEMISTRY, Lyngby, Denmark; 7DTU CHEMISTRY, Kgs. Lyngby, Denmark; 8EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY, Shanghai, China; PAPER: 403/Molten/Keynote (Oral) SCHEDULED: 12:10/Mon./Bossa (150/3rd) ABSTRACT: Spectroscopy is an enabling tool to understand structure-reactivity relationships, that can be applied from predicting toxicity of nanomaterials to engineer better catalytic processes. Operando methodology analyzes both, the catalyst structure and its activity/selectivity simultaneously in a cell that is fit for in situ spectroscopy and performs like a catalytic reactor; correlating structure changes with catalytic performance. Some representative works illustrate this. 1-3 We will present a study on the role of additives, support, coverage, hydration and reaction conditions on the states of supported vanadium and its relevance for catalytic reaction and reducibility. This is applied to assess the molecular basis for activation/deactivation and the nature of the catalyst active site for oxide reduction, alkane oxidative dehydrogenation, ammoxidation and for environmental selective catalytic reduction of NOx. We will also illustrate the capacity of real time spectroscopy to understand reaction mechanism for liquid phase reactions,4 like the role of Brønsted Acid Sites (BAS) vs. that of Lewis Acid Sites (LAS) for the acetalization of glycerol into solketal. Mesoporous cellular foams modified to contain exclusively BAS, LAS and combinations thereof illustrate the role of BAS.4 This relevance led us to use novel Brønsted acid ionic liquids (BAILs).5 The transversal nature of the operando approach places it at the junction between fundamental catalytic chemistry and applied chemical engineering. This work is supported by European Commission BIORIMA GA 760928 and Spanish Ministry RIEN2O, CTM2017-82335-R. References: [1] Calvino-Casilda, V.; Stawicka, K.; Trejda, M.; Ziolek, M.; Banares, M. A. Real-Time Raman Monitoring and Control of the Catalytic Acetalization of Glycerol with Acetone over Modified Mesoporous Cellular Foams. J. Phys. Chem. C 2014, 118 (20). [2] Stawicka, K.; Díaz-Álvarez, A. E.; Calvino-Casilda, V.; Trejda, M.; Banares, M. A.; Ziolek, M. The Role of Brønsted and Lewis Acid Sites in Acetalization of Glycerol over Modified Mesoporous Cellular Foams. J. Phys. Chem. C 2016, 120 (30), 16699–16711. [3] Gui, Z.; Zahrtmann, N.; Saravanamurugan, S.; Reyero, I.; Qi, Z.; Banares, M. A.; Riisager, A.; Garcia-Suarez, E. J. Brønsted Acid Ionic Liquids (BAILs) as Efficient and Recyclable Catalysts in the Conversion of Glycerol to Solketal at Room Temperature. ChemistrySelect 2016, 1 (18). |