Catalytic Spectroscopy Laboratory

Literally, ... catalysis cannot be understood without spectroscopy


Our group stands on spectroscopic understanding of catalysis.



... the scattered radiations enable us to obtain an insight into the ultimate structure of the scattering substance.”


C.V. Raman, Nobel award lecture, 1930




METHODOLOGY - Understand structure-performance relationships in catalysis combining spectroscopy during catalytic reaction with simultaneous activity measurement (i.e., operando methodology, term which we coined in 2000) for real-time MONITORING OF CATALYTIC PROCESSES, CATALYST EVOLUTION and SYNTHESIS. This implies the development of new in situ spectroscopic tools and devices. 


SYSTEMS - Support and interface effect on bulk and dispersed oxides for C1-C5 hydrocarbon valorization into nitriles, oxygenates and olefins; for the valorization of renewables; to investigate fine chemical processes and environmental catalysis. We also investigate catalytic promotion of chemical hydrogen release/storage and process intensification through the use of alternative activation means, such as microwaves, ultrasound, photocatalysis or inductive heating, and how the reaction mechanism is affected by these.

Associate Editorhttp://ees.elsevier.com/cattod
 

Miguel A. Bañares

Madrid, March 2011

We focus in the following research lines:


VERTICAL RESEARCH LINES


  1. Viñeta Catalysis in the C1-C3 chemistry, oxidation and ammoxidation.


  1. Viñeta Acid, base and redox processes. 


  1. Viñeta Operando Raman-GC-MS studies


  1. ViñetaLiquid phase fine chemical and reaction monitoring (Raman)


  1. Viñeta Sustainable chemistry

    - Glycerol to acrylonitrile by reaction with ammonia

    - Glycerol to glycerol carbonate by reaction with urea


  1. Viñeta Environmental applications of catalysis.


  1. Viñeta Structure-activity relationship in catalysis by oxides.


TRANSVERSAL RESEARCH LINE


  1. Viñeta CATALYTIC SPECTROSCOPY, real-time Raman studies


  1. Viñeta IN SITU Raman during temperature-programmed treatments, with online mass spectrometry (e.g., TPR-Raman-MS).


  1. Viñeta OPERANDO Raman spectroscopy during catalytic reaction with simultaneous activity measurement (e.g., Operando Raman-GC-MS during propane ammoxidation)


  1. Viñeta REACTION MONITORING  methodology: In situ spectroscopy during true catalytic operation (e.g., Raman monitoring of Knoevenagel condensation reaction or Raman monitoring of glycerol reactions)

PRESENTATION


Bañares’ group focuses its research on UNDERSTANDING STRUCTURE-PERFORMANCE relationships in catalysis combining spectroscopy during catalytic reaction with simultaneous activity measurement (operando methodology, term which we coined in 2000) for real-time MONITORING OF CATALYTIC PROCESSES, CATALYST EVOLUTION and SYNTHESIS.



METHODOLOGY:

Real-time Catalytic Spectroscopy studies

In situ and operando methodologies inform on the state of the catalyst during reaction, activation, deactivation and reaction monitoring deliver molecular information on reaction evolution.

  1. -IN SITU - We use, spectroscopy under variable-programmed  conditions (e.g., Raman during temperature-programmed treatments, with online mass spectrometry: TPR-Raman-MS)

  2. -OPERANDO spectroscopy during genuine catalytic reaction with simultaneous activity measurement (e.g., Operando Raman-GC-MS during propane ammoxidation)

  3. -REACTION MONITORING, real-time spectroscopy during reaction (e.g., Raman monitoring of Knoevenagel condensation reaction or Raman monitoring of glycerol reactions) or during the synthesis of catalysts (mixed oxides, mesoporous materials, support-stabilized nanoscaled oxides, synthesis of oxide nanotubes).

  4. -Our spectroscopies are essentially Raman, infrared and UV-Vis, which we COMPLEMENT with collaborations using in situ and operando EPR and synchrotron measurements.

  5. -We explore application of operando methodologies to understand structural and catalytic profiles along the channels of honeycomb catalysts, or other SHAPED catalysts.

  6. -We explore AUTOMATION of multiple operando systems

  7. -COLLABORATION with leading DFT groups is integral part of our approach to understand spectra, structure and reactivity. 



SYSTEMS:

  1. -We study SUPPORTED OXIDE CATALYSTS (e.g., V, Nb, Cr, Mo, W oxides on CeO2, SiO2, TiO2, ZrO2, Nb2O5, activated carbon and mesoporous supports, among others).

  2. -We address the relationships BETWEEN SUPPORTED AND MIXED OXIDES. E.g., in situ XANES and EPR and operando Raman-GC studies show that vanadia dispersed on ceria is stabilized as V5+ on Ce3+ in CeO2, mimicking the bulk CeVO4.

  3. -Finally, we address mixed oxides and SUPPORT-STABILIZED NANOSCALED OXIDE CATALYSTS.  Catalysis occurs on the surface, which becomes the predominant factor as the particle size decreases. We use nanoscaled particles, to trigger the surface-to-volume ratio, which are stabilized on microscaled oxide supports. Thus, Al2O3-supported nano-VSbO4 perform like bulk VSbO4 and operando Raman-GC assesses the interplay between dispersed vanadia, segregated SbOx and VSbO4 lattice to activate propane and ammonia during ammoxidation. We confirm the need of segregated dispersed vanadia with DFT calculation on NH3, C2 and C3 alkanes and alkenes activation on the surface of VSbO4.

  4. -We investigate the role of promoters (e.g., Nb, P, Sb) in the systems described above for the reactions listed below.

  5. -We investigate hydrides for energy storage/release, such a ammonia borane and related compounds.




REACTIONS/SYNTHESES:

the systems and methodologies described above are used to develop and understand catalysts for gas, vapor and liquid phase reactions.

  1. -Light C1-C5 hydrocarbon valorization into nitrile, oxygenates and olefins, such as the ammoxidation of propane to acrylonitrile.

  2. -Valorization of renewables, such as conversion of glycerol into acrylonitrile (discovered by our group) and carbonylation into glycerol carbonate or preparation of glycidol.

  3. -Environmental catalysis

  4. -Investigation of reaction pathway and real-time monitoring of fine chemistry reactions; e.g., Knoevenagel condensation, Michael addition or alkylation reactions in aqueous and dry media, also with ionic liquids.

  5. -Recently, we are addressing process intensification through the use of alternative activation means, such as microwaves, ultrasound, photocatalysis or inductive heating, and how the reaction mechanism is affected by these.



SPIN-OFF

In 2011, we created a spin-off company AD-Particles (http://www.ad-particles.com) in collaboration with researchers from Instituto de Cerámica y Vidrio and institute for Microelectronics based on the methodology to hierarchicaly disperse nanoparticles on microparticles.



INTERNATIONALIZATION AND NETWORKING

We are very active FOSTERING COMPLEMENTARITY IN RESEARCH through international and national collaboration and organizing events to entangle research groups, like the Operando Conference series (which Bañares co-founded); Bañares’ vision in reflected in the Memorandum of Understanding of the ESF COST Action D36 (2006-2011) (http://www.cost.eu/domains_actions/cmst/Actions/D36 ), which he proposed and chaired. More recently, he has been involved in the preparation of COST Action TD1204 MODENA (http://www.cost.eu/domains_actions/mpns/Actions/TD1204 ) on the toxicity of nanoparticles, which he vice-chairs.